Non-Noble Metal Catalysis E-Book

• Herausgeber: Wiley-VCH Verlag GmbH & Co. KGaA
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1023

Veröffentlichungsjahr: 2018

Beschreibung

An expert overview of current research, applications, and economic and environmental advantages

The study and development of new homogeneous catalysts based on first-row metals (Mn, Fe, Co, Ni, and Cu) has grown significantly due to the economic and environmental advantages that non-noble metals present. Base metals offer reduced cost, greater supply, and lower toxicity levels than noble metals?enabling greater opportunity for scientific investigation and increased development of practical applications. Non-Noble Metal Catalysis provides an authoritative survey of the field, from fundamental concepts and computational methods to industrial applications and reaction classes.

Recognized experts in organometallic chemistry and homogeneous catalysis, the authors present a comprehensive overview of the conceptual and practical aspects of non-noble metal catalysts. Examination of topics including non-innocent ligands, proton-coupled electron transfer, and multi-nuclear complexes provide essential background information, while areas such as kinetic lability and lifetimes of intermediates reflect current research and shifting trends in the field. This timely book demonstrates the efficacy of base metal catalysts in the pharmaceutical, fine-chemical, and agrochemical industries, addressing both environmental and economic concerns.

Providing essential conceptual and practical exploration, this valuable resource:

-Illustrates how unravelling new reactivity patterns can lead to new catalysts and new applications
-Highlights the multiple advantages of using non-noble metals in homogenous catalysis
-Demonstrates how the availability of non-noble metal catalysis reduces costs and leads to immense savings for the chemical industry
-Reveals how non-noble metal catalysis are more sustainable than noble metals such as palladium or platinum

Non-Noble Metal Catalysis: Molecular Approaches and Reactions is an indispensable source of up-to-date information for catalytic chemists, organic chemists, industrial chemists, organometallic chemists, and those seeking to broaden their knowledge of catalytic chemistry.

Leseprobe

Table of Contents

Cover

Preface

References

1 Application of Stimuli‐Responsive and “Non‐innocent” Ligands in Base Metal Catalysis

1.1 Introduction

1.2 Stimuli‐Responsive Ligands

1.3 Redox‐Active Ligands as Electron Reservoirs

1.4 Cooperative Ligands

1.5 Substrate Radicals in Catalysis

1.6 Summary and Conclusions

References

2 Computational Insights into Chemical Reactivity and Road to Catalyst Design: The Paradigm of CO

2

Hydrogenation

2.1 Introduction

2.2 Reaction Energetics and Governing Factor

2.3 Newly Designed Catalysts and Their Reactivity

2.4 Correlation Between Hydricity and Reactivity

2.5 Concluding Remarks

Acknowledgments

References

3 Catalysis with Multinuclear Complexes

3.1 Introduction

3.2 Stoichiometric Reaction Pathways

3.3 Application in Catalysis

3.4 Polynuclear Complexes

3.5 Outlook

Acknowledgments

References

4 Copper‐Catalyzed Hydrogenations and Aerobic NN Bond Formations: Academic Developments and Industrial Relevance

4.1 Introduction

4.2 Cu‐Promoted NN Bond Formation

4.3 Cu‐Catalyzed Homogeneous Hydrogenation

4.4 Conclusions

References

5 CC Hydrogenations with Iron Group Metal Catalysts

5.1 Introduction

5.2 Iron

5.3 Cobalt

5.4 Nickel

5.5 Conclusion

Acknowledgments

References

6 Base Metal‐Catalyzed Addition Reactions Across CC Multiple Bonds

6.1 Introduction

6.2 Catalytic Addition to Alkenes Initiated Through Radical Mechanisms

6.3 Other Catalytic Additions to Unsaturated Bonds Proceeding Through Initial R (R ≠ H) Attack

6.4 Catalytic Addition to Alkenes Initiated Through Polar Mechanisms

6.5 Hydrosilylation Reactions

6.6 Conclusion

References

7 Iron‐Catalyzed Cyclopropanation of Alkenes by Carbene Transfer Reactions

7.1 Introduction

7.2 Achiral Iron Porphyrin Catalysts

7.3 Chiral Iron Porphyrin Catalysts

7.4 Iron Phthalocyanines and Corroles

7.5 Iron Catalysts with N or N,O Ligands

7.6 The [Cp(CO)

2

Fe(THF)]BF

4

Catalyst

7.7 Conclusions

References

8 Novel Substrates and Nucleophiles in Asymmetric Copper‐Catalyzed Conjugate Addition Reactions

8.1 Introduction

8.2 Catalytic Asymmetric Conjugate Additions to α‐Substituted α,β‐Unsaturated Carbonyl Compounds

8.3 Catalytic Asymmetric Conjugate Additions to Alkenyl‐heteroarenes

8.4 Conclusion

References

9 Asymmetric Reduction of Polar Double Bonds

9.1 Introduction

9.2 Manganese

9.3 Iron

9.4 Cobalt

9.5 Nickel

9.6 Copper

9.7 Conclusion

References

10 Iron‐, Cobalt‐, and Manganese‐Catalyzed Hydrosilylation of Carbonyl Compounds and Carbon Dioxide

10.1 Introduction

10.2 Hydrosilylation of Aldehydes and Ketones

10.3 Reduction of Imines and Reductive Amination of Carbonyl Compounds

10.4 Reduction of Carboxylic Acid Derivatives

10.5 Hydroelementation of Carbon Dioxide

10.6 Conclusion

References

11 Reactive Intermediates and Mechanism in Iron‐Catalyzed Cross‐coupling

11.1 Introduction

11.2 Cross‐coupling Catalyzed by Simple Iron Salts

11.3 TMEDA in Iron‐Catalyzed Cross‐coupling

11.4 NHCs in Iron‐Catalyzed Cross‐coupling

11.5 Phosphines in Iron‐Catalyzed Cross‐coupling

11.6 Future Outlook

Acknowledgments

References

12 Recent Advances in Cobalt‐Catalyzed Cross‐coupling Reactions

12.1 Introduction

12.2 Cobalt‐Catalyzed CC Couplings Through a CH Activation Approach

12.3 Cobalt‐Catalyzed CC Couplings Using a Preactivated Substrate Approach (Aryl Halides and Pseudohalides)

12.4 Cobalt‐Catalyzed CX Couplings Using CH Activation Approaches

12.5 Cobalt‐Catalyzed CX Couplings Using a Preactivated Substrate Approach (Aryl Halides and Pseudohalides)

12.6 Miscellaneous

12.7 Conclusions and Future Prospects

Acknowledgments

References

13 Trifluoromethylation and Related Reactions

13.1 Trifluoromethylation Reactions

13.2 Trifluoromethylthiolation Reactions

13.3 Perfluoroalkylation Reactions

13.4 Conclusion

References

14 Catalytic Oxygenation of CC and CH Bonds

14.1 Introduction

14.2 Oxygenation of CC Bonds

14.3 Oxygenation of CH Bonds

14.4 Conclusions and Outlook

Acknowledgment

References

15 Organometallic Chelation‐Assisted C−H Functionalization

15.1 Introduction

15.2 CC Bond Formation via CH Activation

15.3 CHeteroatom Formation via CH Activation

15.4 Conclusions

Acknowledgments

References

16 Catalytic Water Oxidation: Water Oxidation to O

2

Mediated by 3d Transition Metal Complexes

16.1 Water Oxidation – From Insights into Fundamental Chemical Concepts to Future Solar Fuels

16.2 Model Well‐Defined Water Oxidation Catalysts

16.3 Conclusion and Outlook

References

17 Base‐Metal‐Catalyzed Hydrogen Generation from Carbon‐ and Boron Nitrogen‐Based Substrates

17.1 Introduction

17.2 Hydrogen Generation from Formic Acid

17.3 Hydrogen Generation from Alcohols

17.4 Hydrogen Storage in Liquid Organic Hydrogen Carriers

17.5 Dehydrogenation of Ammonia Borane and Amine Boranes

17.6 Conclusion

References

18 Molecular Catalysts for Proton Reduction Based on Non‐noble Metals

18.1 Introduction

18.2 Iron and Nickel Catalysts

18.3 Other Non‐noble Metal‐Based Catalysts: Co, Mn, Cu, Mo, and W

18.4 Conclusion

References

19 Nonreductive Reactions of CO

2

Mediated by Cobalt Catalysts: Cyclic and Polycarbonates

19.1 Introduction

19.2 Cocatalysts for CO

2

/Epoxide Couplings: Salen‐Based Systems

19.3 Co–Porphyrins as Catalysts for Epoxide/CO

2

Coupling

19.4 Cocatalysts Based on Other N

4

‐Ligated and Related Systems

19.5 Aminophenoxide‐Based Co Complexes

19.6 Conclusion and Outlook

Acknowledgments

References

20 Dinitrogen Reduction

20.1 Introduction

20.2 Activation of N

2

20.3 Reduction of N

2

to Ammonia

20.4 Reduction of N

2

to Silylamines

20.5 Conclusions and Outlook

Acknowledgments

References

Index

End User License Agreement

List of Tables

Chapter 2

Table 2.1 Intrinsic reaction barriers (ΔG

‡

) for Co(III)‐ and Fe(II)‐based ...

Chapter 3

Table 3.1 Selected examples of non‐noble multimetallic clusters and their cataly...

Chapter 4

Table 4.1 Cu catalysts for the hydrogenation of CO

2

.

Table 4.2 Cu catalysts for the hydrogenation of carbonyl compounds.

Table 4.3 Cu catalysts for the semihydrogenation of alkynes.

Chapter 5

Table 5.1 Comparison of

7

with various precious metal catalysts in the hydrogenat...

Table 5.2 Comparison of complexes

7

–

11

in the hydrogenation of sterically hindere...

Table 5.3 Selected examples of the (

E

)‐selective alkyne hydrogenation with

12

.

Table 5.4 Hydrogenation of various

N

‐heterocycles with

14

.

Table 5.5 Hydrogenation of various styrenes with

14

.

Table 5.6 Comparative hydrogenation with iron complexes

17

,

18

, and

19

.

Table 5.7 Hydrogenation of prochiral styrenes with

(

S

)‐25

.

Table 5.8 Enantioselective hydrogenation of exo‐ and endocyclic alkenes with

(S)‐

...

Table 5.9 Hydrogenation of 1,1‐diarylethenes with

27

.

Table 5.11 Alkene hydrogenation with precatalyst

30

.

Table 5.12 Comparative hydrogenation of alkenes with

34

–

38

.

Table 5.13 Selected bis(phosphine) ligands in enantioselective cobalt‐catalyzed ...

Table 5.14 Hydrogenation of oxygen‐containing alkenes with

42

.

Table 5.15 Hydrogenation of alkenes with

43

.

Table 5.16 Hydrogenation of terminal alkenes with the nickel complexes

46

and

50

....

Chapter 6

Table 6.1 Ni‐catalyzed, Lewis‐acid‐assisted carbocyanation of alkynes.

Chapter 8

Table 8.1 Cu(I)‐catalyzed enantioselective addition of Grignard reagent to 2‐sty...

Chapter 11

Table 11.1 Evaluation of low‐valent precatalysts

1

and

2

by Fürstner and coworker...

Table 11.2 Examples of iron‐catalyzed cross‐coupling reactions with TMEDA as an ...

Table 11.3 Representative examples of iron‐catalyzed cross‐coupling reactions us...

Table 11.4 Alkyl–alkyl cross‐coupling with iron salts and NHC additives by Cárde...

Chapter 20

Table 20.1 Activity of transition metal chlorides in silylation of dinitrogen.

List of Illustrations

Chapter 1

Scheme 1.1 Switching catalytic properties of a catalyst using external s...

Figure 1.1 Titanium‐based redox‐switchable catalyst (a) and the effect ...

Figure 1.2 Ferrocene containing redox‐switchable catalysts (a) and inver...

Figure 1.3 Proton‐switchable copper catalyst.

Figure 1.4 Reversible deprotonation of a 4,7‐dihydroxy‐1,10‐phenanthroli...

Figure 1.5 Light‐active scaffolds that undergo structural changes upon i...

Figure 1.6 Light‐induced enantioselective cyclopropanation.

Scheme 1.2 (a) Classic oxidative addition and (b) oxidative addition in ...

Scheme 1.3 Bis(imino)pyridine complex (left), mono‐reduced (middle), and...

Figure 1.7 Bis(imino)pyridyl complexes used in the polymerization of eth...

Figure 1.8 Ligand‐mediated oxidative addition.

Figure 1.9 Family of BIP‐related complexes (

H

−

M

) for the hydrogenation o...

Scheme 1.4 Ligand‐mediated cycloaddition reactions.

Figure 1.10

N

,

P

Catalysts for hydrosilylation of alkenes.

Scheme 1.5 Catechol‐derived redox non‐innocent ligands reported in liter...

Scheme 1.6 Substrate activation by a cooperative ligand: (a) substrate a...

Scheme 1.7 Key steps in substrate activation and catalysis by the enzyme...

Figure 1.11 (a) Cu(II)–thiophenol‐based catalyst described by Wieghardt ...

Scheme 1.8 Catalytic cycle for alcohol oxidation by salen complexes.

Scheme 1.9 Cooperative activation and oxidation of methanol over an iron...

Figure 1.12 Cooperative activation of formaldehyde by an iron–pincer com...

Figure 1.13 Dihydrogen cleavage catalyzed by a metal‐pendant nitrogen‐ba...

Figure 1.14 One‐electron substrate activation and subsequent controlled ...

Figure 1.15 Electron transfer from metal to substrate (transformation of...

Scheme 1.10 First example of a carbene radical complex by Casey and cowo...

Scheme 1.11 Examples of metalloradical Co(por)‐catalyzed reactions with ...

Scheme 1.12 Formation of bis‐nitrene (left) and mono‐nitrene (right) rad...

Scheme 1.13 Examples of metalloradical Co(Por)‐catalyzed reactions with ...

Chapter 2

Figure 2.1 (a) Schematic free energy profile of a reaction. (b) Illustr...

Figure 2.2 (a) π‐Type molecular orbitals of CO

2

at different OCO angles....

Figure 2.3 CO

2

hydrogenation via hydride transfer by transition metal ca...

Figure 2.4 Proposed catalytic cycle exhibited by iron complex R

Fe

.

Figure 2.5 DLPNO‐CCSD(T) free energy profile of key reaction steps for R

Figure 2.6 Newly designed Fe(II)‐ and Co(III)‐based complexes.

Figure 2.7 Correlation plots for the H

2

‐splitting step: (a) correlation ...

Figure 2.8 Correlation plots for the hydride transfer step: (a) correlat...

Figure 2.9 Plot correlating both the barriers (H

2

‐splitting and hydride ...

Chapter 3

Figure 3.1 Binding and activation of unsaturated substrates (a) at a si...

Figure 3.2 Bifunctional CO

2

binding and activation by Co…M cooperation, ...

Figure 3.3 Bimetallic N

2

binding and activation by Co–M complexes, repor...

Figure 3.4 Bimetallic alkyne binding and activation by quintuply bonded ...

Figure 3.5 Oxidative addition and reductive elimination reactions (a) at...

Figure 3.6 Bimetallic H

2

addition and elimination reactions with polariz...

Figure 3.7 Bimetallic E–H addition and elimination reactions reported by...

Figure 3.8 Bimetallic C–X reactions: (a) C–X activation by Mankad and (b...

Figure 3.9 Bimetallic C



O cleavage products reported by (a) Pete...

Figure 3.10 Bimetallic catalysis for alkyne cyclotrimerization: (a) ster...

Figure 3.11 Heterobimetallic catalysis proceeding by bimetallic oxidativ...

Figure 3.12 Lewis‐acid‐assisted catalysis for (a) formic acid dehydrogen...

Figure 3.13 Cooperative small‐molecule reduction: (a) electrocatalytic n...

Figure 3.14 Cooperative mechanisms for (a) epoxide carbonylation studied...

Figure 3.15 Two‐ and four‐electron redox processes exhibited by a trinuc...

Chapter 4

Scheme 4.1 Pyrazoline formation via oxidative coupling of oxime esters a...

Scheme 4.2 1,1′‐Bibenzimidazole formation via aerobic cyclodehydrogenati...

Scheme 4.3 Approaches to obtain azines from nitriles or ketones.

Scheme 4.4 Jiao protocol for copper‐catalyzed aerobic dehydrogenative co...

Scheme 4.5 Unusual diazo compound formation via aerobic dehydrogenative ...

Scheme 4.6 Two mechanisms proposed for 1,2,4‐triazole formation from an ...

Scheme 4.7 Tautomers that yield NN bond containing five‐membered aromat...

A structural overview of aromatic

N

‐heterocyclic product classes acce...

Scheme 4.8 General catalytic cycle for Cu‐based hydrogenation.

Chapter 5

Figure 5.1 Technical products from homogeneous C



C hydrogenat...

Figure 5.2 Active sites of various hydrogenases (Cys, cysteine; GMP, gua...

Figure 5.3 Publications per year for the search terms “nickel,” “cobalt,...

Scheme 5.1 Generation of Ziegler‐type hydrogenation catalysts and simila...

Scheme 5.2 Synthesis of iron(II)‐alkyl

P

,

P

,

P

pincer complexes.

Scheme 5.3 Mechanism of hydrogenation proposed by Peters et al. [18].

Scheme 5.4 Synthesis of bis(imino)pyridine iron complex

7

.

Scheme 5.5 Mechanistic proposal of alkene hydrogenation with

7

according...

Figure 5.4 Modified bis(imino)pyridine and bis(NHC)pyridine iron complex...

Scheme 5.6 Synthesis of

P

,

N

,

P

pincer iron complex

12

by Milstein et al. ...

Scheme 5.7 Aliphatic

P

,

N

,

P

‐complex

13

and possible key intermediates in ...

Scheme 5.8 Synthesis of potassium bis(anthracene)ferrate

17

.

Figure 5.5 Cyclopentadienyl iron complexes

18

and

19

.

Scheme 5.9 Generation of Ziegler‐type Co/Al hydrogenation catalysts.

Scheme 5.10 Synthesis of alkyl bis(imino)pyridine cobalt complex

22

.

Scheme 5.11 Mechanistic proposal of catalytic hydrogenation with

22

.

Scheme 5.12 Synthesis of chiral bis(imino)pyridine methyl cobalt

(S)‐25

...

Scheme 5.13 Competing cyclometalation of active cobalt hydride intermedi...

Figure 5.6 Oxazoline iminopyridine complex

27

.

Figure 5.7 Bis(arylimidazol‐2‐ylidene)pyridine cobalt methyl

28

.

Scheme 5.14 Reactivity of

28

with dihydrogen and sequential H‐atom migra...

Scheme 5.15 Formation of cationic pincer catalyst

31

by protonation of

3

...

Scheme 5.16 Synthesis and reversible hydrogen addition of

P

,

B

,

P

pincer c...

Scheme 5.17 Synthesis of potassium bis(anthracene) cobaltate

34

.

Scheme 5.18 Proposed mechanism for catalytic hydrogenation with

34

.

Figure 5.8 Heteroleptic arene/alkene cobaltate complexes

35

–

38

.

Scheme 5.19 Synthesis of tetrameric cobalt complex

39

.

Scheme 5.20 Enantioselective alkene hydrogenation with

(

R

,

R

)‐40

(a...

Figure 5.9 Bisphosphine cobalt(II) dialkyl cobalt(II) complexes

41

,

42

, ...

Scheme 5.21 Proposed olefin hydrogenation mechanism for precatalyst

42

. ...

Figure 5.10 Aminosalen‐type nickel(II) complexes

43

,

44

, and

45

.

Scheme 5.22 Synthesis of

P,N,P

‐nickel(II) hydride

46

.

Scheme 5.23 Stability of

P

,

N

,

P

nickel(II) methyl complex

47

.

Scheme 5.24 Synthesis of borylnickel complex

48

and reversible addition ...

Scheme 5.25 Synthesis of

P

,

B

,

P

nickel(I) hydride

50

.

Figure 5.11 The bidentate diphosphine nickel(II) complex

51

.

Scheme 5.26 Synthesis of the tetrameric nickel(I) complex

52

.

Chapter 6

Scheme 6.1 Mukaiyama hydration of olefins.

Scheme 6.2 Hydrogen atom transfer (HAT) mechanism for the Markovnikov hy...

Scheme 6.3 Co‐catalyzed hydrohydrazination reaction.

Scheme 6.4 Preparation of propargylic hydrazines from enynes by catalyti...

Scheme 6.5 Mn‐ and Co‐catalyzed hydrohydrazination of olefins. Selected ...

Scheme 6.6 (a) Co‐catalyzed hydroazidation of unactivated olefins. (b) O...

Scheme 6.7 Cobalt‐catalyzed hydrocyanation of olefins.

Scheme 6.8 Cobalt‐catalyzed hydrochlorination of olefins.

Scheme 6.9 Stoichiometric hydrofunctionalization of alkenes mediated by ...

Scheme 6.10 Co‐catalyzed hydrofluorination of unactivated olefins.

Scheme 6.11 Co‐catalyzed Markovnikov hydroalkoxylation of olefins.

Scheme 6.12 Fe‐catalyzed hydromethylation of olefins.

Scheme 6.13 One‐step synthesis of an intermediate of a glucocorticoid re...

Figure 6.1 Amino‐bis(phenolate) Fe

III

catalyst precursor for the hydroa...

Scheme 6.14 Dual‐catalytic hydroarylation of olefins. Isolated yields of...

Scheme 6.15 Mn‐catalyzed, aerobic oxidative hydroxyazidation of olefins....

Scheme 6.16 Proposed catalytic cycle for the Mn‐catalyzed, aerobic oxida...

Scheme 6.17 Aminohydroxylation of olefins catalyzed by Fe

II

phthalocyani...

Scheme 6.18 Proposed reaction mechanisms for the aminohydroxylation reac...

Scheme 6.19 The Cu‐catalyzed hydroamination of styrenes.

Scheme 6.20 Hydroamination of unactivated, 1,1‐disubstituted alkenes. Se...

Scheme 6.21 Copper‐catalyzed asymmetric hydroamination of unactivated in...

Scheme 6.22 (a) Direct and reductive hydroamination reactions of alkynes...

Scheme 6.23 Proposed mechanism for the Ni‐catalyzed, Lewis‐acid‐assisted...

Scheme 6.24 Catalytic transfer hydrocyanation reaction. (a) Late‐stage f...

Scheme 6.25 Anti‐Markovnikov hydrosilylation reaction catalyzed by the F...

Scheme 6.26 Anti‐Markovnikov hydrosilylation reaction of functionalized ...

Scheme 6.27 Chalk–Harrod mechanism for the hydrosilylation reaction.

Scheme 6.28 Proposed mechanism for the anti‐Markovnikov hydrosilylation ...

Scheme 6.29 Anti‐Markovnikov hydrosilylation and isomerization/hydrosily...

Scheme 6.30 Selected examples of products of regiodivergent hydrosilylat...

Scheme 6.31 (a) Markovnikov hydrosilylation reaction of terminal alkynes...

Scheme 6.32 Markovnikov hydroboration reaction of α‐vinylsilanes.

Scheme 6.33 Anti‐Markovnikov hydrosilylation of olefins catalyzed by Fe ...

Chapter 7

Figure 7.1 Approximate number of publications dealing with the catalyti...

Scheme 7.1 General synthesis of iron‐catalyzed cyclopropanation of alken...

Figure 7.2 The core structure of a porphyrin molecule.

Scheme 7.2 Fe

II

(TTP) (

1

)‐catalyzed alkene cyclopropanation.

Scheme 7.3 Cyclopropane diastereoisomers and products of diazo dimerizat...

Scheme 7.4 Suggested alkene cyclopropanation mechanism.

Scheme 7.5 Synthesis and molecular structure of Fe(F

20

TPP)(CPh

2

) (

2

). ...

Scheme 7.6 Cyclopropanation of styrenes catalyzed by the Fe

III

(porp)Cl/C...

Scheme 7.7 Cyclopropanation of alkenes in a biphasic medium.

Scheme 7.8 Cyclopropanation of styrenes, dienes, and enynes by using tri...

Scheme 7.9 Cyclopropanation of alkenes by using Ph

2

S

+

CH

2

CF

3

·

−

O...

Scheme 7.10 Proposed mechanism for the cyclopropanation of alkenes by us...

Scheme 7.11 Fe(TPP)Cl‐catalyzed cyclopropanation of alkenes by using Ph

2

Scheme 7.12 Cyclopropanation of alkenes by using glycine ethyl ester hyd...

Scheme 7.13 Cyclopropanation of alkenes by using aminoacetonitrile hydro...

Scheme 7.14

D

2

‐symmetrical porphyrin iron(III) catalyst

15

and iron ...

Figure 7.3 Cyclopropanes synthesized in the presence of catalyst

16

.

Scheme 7.15 Proposed mechanism of complex

16

‐catalyzed alkene cyclopropa...

Scheme 7.16 Cyclopropanation of styrenes by (PhCO)CHN

2

and CF

3

CHN

2

catal...

Figure 7.4

D

2

‐symmetrical iron(III) chiral porphyrin

19

.

Scheme 7.17

C

2

‐symmetrical iron(III) chiral porphyrin

20

.

Figure 7.5

C

2

‐symmetrical iron(III) chiral porphyrins

21

and

22

.

Figure 7.6 Iron phthalocyanine complexes

23

–

28

used as cyclopropanation ...

Scheme 7.18 Synthesis of

C

‐silyl cyclopropanes catalyzed by complex

23

. ...

Scheme 7.19 Cyclopropanation of styrene by EDA using catalysts

24

–

28

.

Scheme 7.20 Synthesis and molecular structure of Fe

IV

(tpfc) (

29

).

Scheme 7.21 Synthesis of Fe

IV

(tpfc) (

29

), Fe

III

(tpfc)(OEt

2

)

2

(

30

), Fe

III

Scheme 7.22 Cyclopropanation of styrene catalyzed by iron corroles

29

–

32

Figure 7.7 Iron(II) tetraaza macrocyclic complexes

33

–

36

used as cyclopr...

Figure 7.8 Cyclopropanes synthesized in the presence of catalysts

33

–

36

....

Figure 7.9 Ligands

37

–

42

used in Fe‐mediated cyclopropanation catalysis....

Scheme 7.23 Cyclopropanation of styrene by EDA catalyzed by iron complex...

Figure 7.10 Chiral spiro‐

bis

oxazoline ligands

43

–

49

used in combination ...

Scheme 7.24 Asymmetric synthesis of chiral [3.1.0]bicycloalkane lactones...

Scheme 7.25 Asymmetric intramolecular cyclopropanation of indoles cataly...

Figure 7.11 Complex

50

‐catalyzed synthesis of cyclopropanes.

Figure 7.12 Complex

51

‐catalyzed synthesis of cyclopropanes.

Scheme 7.26 Mechanistic proposal for the

51

‐catalyzed cyclopropanation. ...

Chapter 8

Scheme 8.1 Copper(I)‐catalyzed addition of nucleophiles to α,β‐unsaturat...

Scheme 8.2 Copper‐catalyzed asymmetric conjugate addition of alkylalumin...

Scheme 8.3 Copper‐NHC‐catalyzed asymmetric conjugate addition of Grignar...

Scheme 8.4 Cu(I)‐catalyzed asymmetric conjugate addition of Grignard rea...

Scheme 8.5 Conjugate addition followed by α‐alkylation in MTBE/DMPU (3.5...

Figure 8.1 A selection of the products obtained via asymmetric conjugat...

Scheme 8.6 Natural product syntheses in which sequential asymmetric conj...

Figure 8.2 (a) Different heteroarenes, (b) alkenyl‐heteroarene vs α,β‐un...

Scheme 8.7 Different strategies for conjugate nucleophilic addition to a...

Scheme 8.8 Enantioselective copper‐catalyzed reduction of β,β‐disubstitu...

Scheme 8.9 Reactivity comparison between 4‐ and 3‐alkenylpyridine.

Scheme 8.10 Copper‐catalyzed asymmetric conjugate reduction of a 2‐alken...

Scheme 8.11 Copper‐catalyzed reductive coupling reactions of vinyl‐heter...

Scheme 8.12 Copper‐catalyzed reductive coupling reactions of vinyl‐heter...

Scheme 8.13 Copper‐catalyzed borylative coupling of vinyl‐heteroarenes a...

Scheme 8.14 Ni‐catalyzed Grignard addition.

Scheme 8.15 Enantioselective addition of Grignard reagents to alkenyl‐he...

Scheme 8.16 Grignard scope on benzoxazole‐ and pyrimidine‐derived substr...

Chapter 9

Scheme 9.1 Manganese(I) chiral ATH (a) and AH (b, c) precatalysts.

Scheme 9.2 Gao's pioneering iron(II)‐based catalytic system.

Scheme 9.3 Morris' first‐generation iron/PNNP ATH catalyst.

Scheme 9.4 Morris' second‐generation iron/PNNP ATH catalysts.

Scheme 9.5 Activation mechanism of Morris' second‐generation iron/PNNP A...

Scheme 9.6 Morris' third‐generation iron/PNNP ATH catalysts.

Scheme 9.7 Reiser's iron(II) ATH catalyst based on chiral bidentate ison...

Scheme 9.8 Wills' “cyclone”‐type catalyst in the ATH of acetophenone.

Scheme 9.9 Gao's chiral (NH)

4

P

2

macrocycle/Fe(0) in situ catalyst for th...

Scheme 9.10 Mezzetti's chiral N

2

P

2

macrocyclic ATH precatalysts.

Scheme 9.11 Berkessel's photoactivated Shvo‐type, half‐sandwich Fe(0) AH...

Scheme 9.12 Piarulli's and Gennari's half‐sandwich Fe(0) AH catalyst.

Scheme 9.13 Beller's AH catalyst based on an achiral catalyst/chiral ani...

Scheme 9.14 Anion‐assisted H

2

activation with Beller's half‐sandwich cat...

Scheme 9.15 PNP and PN(H)P pincer AH catalysts.

Scheme 9.16 Nishiyama's catalysts for the asymmetric hydrosilylation of ...

Scheme 9.17 Chirik's iron(II) AHS catalyst based on chiral tridentate NN...

Scheme 9.18 Gade's iron(II) AHS catalyst with anionic NNN pincer ligands...

Scheme 9.19 Huang's NNN pincer AHS catalyst.

Scheme 9.20 Ohgo's pioneering cobaloxime/quinine catalytic system for th...

Scheme 9.21 Stereochemical course of benzil asymmetric hydrogenation by ...

Scheme 9.22 Gao's cobalt(I) catalyst for the AH of ketones.

Scheme 9.23 Cobalt‐based catalysts for the AHS of ketones.

Scheme 9.24 Mukaiyama's β‐ketoiminato cobalt(II) catalyst for asymmetric...

Scheme 9.25 Intermediate of the BH

4

−

ketone reduction by β‐ketoi...

Scheme 9.26 Borohydride reduction of 1,3‐diketones by β‐ketoiminato coba...

Scheme 9.27 Cobalt(II) β‐ketoiminato catalysts for the BH

4

−

redu...

Scheme 9.28 Hamada's nickel(II) AH catalyst for chirally labile α‐amino‐...

Scheme 9.29 Gao's nickel(II)/N

2

O

2

P catalyst for the ATH of ketones.

Scheme 9.30 Nickel(II)‐catalyzed ATH of hydrazones and reductive aminati...

Scheme 9.31 Nickel(II)‐catalyzed AHS of electron‐poor aryl alkyl ketones...

Scheme 9.32 Nickel(II)‐catalyzed borohydride reduction of α‐amino ketone...

Scheme 9.33 Nickel‐catalyzed asymmetric borane reduction of α,β‐unsatura...

Scheme 9.34 Copper(I)‐ and copper(II)‐catalyzed AH of ketones with chira...

Scheme 9.35 Johnson's copper‐catalyzed AH of ketones.

Scheme 9.36 List's copper‐catalyzed reduction of α‐ketoesters with Hantz...

Scheme 9.37 Lipshutz's copper‐catalyzed AHS of ketones and phosphinoyl b...

Scheme 9.38 Riant's CuF

2

‐catalyzed AHS of ketones under aerobic and mild...

Scheme 9.39 Beller's Cu(OAc)/monodentate phosphine catalyst for the AHS ...

Scheme 9.40 Gawley's copper(I)/NCH catalyst for the AHS of ketones.

Chapter 10

Figure 10.1 Ligands for iron‐catalyzed hydrosilylation of ketones.

Figure 10.2 Well‐defined iron complexes for catalyzed hydrosilylation of...

Figure 10.3 Well‐defined iron pincer complexes for catalyzed hydrosilyla...

Figure 10.4 Chiral iron complexes for catalyzed asymmetric hydrosilylati...

Figure 10.5 Piano‐stool cyclopentadienyl phosphine iron complexes.

Figure 10.6 Diversity of the NHC ligands for Fe‐NHC‐catalyzed hydrosilyl...

Figure 10.7 Selection of catalytically active iron complexes in hydrosil...

Figure 10.8 Cobalt complexes in hydrosilylation.

Figure 10.9 Ligands and complex for cobalt‐catalyzed asymmetric hydrosil...

Figure 10.10 Efficient manganese complexes for catalytic hydrosilylation...

Figure 10.11 Multidentate ligand Mn complexes for catalytic hydrosilylat...

Scheme 10.1 Iron‐catalyzed hydrosilylation of imines.

Scheme 10.2 Piano‐stool phosphanyl‐pyridine iron‐catalyzed DRA.

Scheme 10.3 Iron‐catalyzed isomerization/DRA reaction.

Scheme 10.4 Cobalt‐phthalocyanine‐catalyzed DRA reaction.

Scheme 10.5 Iron catalysts for chemoselective hydrosilylation of carboxa...

Scheme 10.6 Iron‐catalyzed reduction of primary amides to primary amines...

Scheme 10.7 Iron‐catalyzed hydrosilylation of ureas.

Scheme 10.8 Iron‐catalyzed hydrosilylation of esters to alcohols.

Scheme 10.9 Iron‐catalyzed hydrosilylation of esters to ethers.

Scheme 10.10 Iron‐catalyzed hydrosilylation of esters to aldehydes and l...

Scheme 10.11 Manganese‐catalyzed reduction of esters.

Scheme 10.12 Chemoselective iron‐catalyzed hydrosilylation of carboxylic...

Scheme 10.13 Fe(acac)

2

/P(CH

2

CH

2

Ph

2

)

3

catalyst for reductive functionaliz...

Scheme 10.14 Pincer cobalt complexes for catalyzed hydrosilylation of CO

Scheme 10.15 Iron‐catalyzed hydroboration of CO

2

.

Scheme 10.16 Iron‐catalyzed hydroboration/functionalization of CO

2

.

Scheme 10.17 Iron‐ and cobalt‐catalyzed hydroboration of CO

2

.

Chapter 11

Scheme 11.1 Representative examples of C–C cross‐coupling reactions usin...

Scheme 11.2 Mechanistic proposals for C–C cross‐coupling reactions catal...

Scheme 11.3 (a and b) Synthesis of homoleptic methylated and phenylated ...

Figure 11.1 (a) Synthesis of homoleptic ferrates

5

and

6

using MeMgBr in...

Figure 11.2 (a) Reactivity of

6

with β‐bromostyrene in the absence and p...

Scheme 11.4 (a) Proposed catalytic cycle of the cross‐coupling of

n

‐octy...

Scheme 11.5 Reactivity of well‐defined iron(II)‐NHC complexes reported b...

Scheme 11.6 Precatalyst and model intermediates used by Tonzetich and co...

Scheme 11.7 Catalytic proposals for iron‐NHC‐catalyzed cross‐coupling by...

Scheme 11.8 Representative examples of C–C cross‐coupling reactions usin...

Scheme 11.9 Mechanistic proposal by Nakamura and coworkers for iron‐SciO...

Figure 11.3 (a) Iron‐SciOPP‐catalyzed cross‐coupling of MesMgBr with pri...

Figure 11.4 (a) Reaction of

19

with

n

‐decyl bromide to form cross‐couple...

Figure 11.5 (a) Generation of phenylated iron(II)‐SciOPP species using P...

Scheme 11.10 (a) Synthesis of dpbz‐ and dppe‐supported iron(I) species b...

Chapter 12

Scheme 12.1 (a) Early Co(0)‐catalyzed annulation of

N

‐benzylideneaniline...

Scheme 12.2 Ternary catalyst system reported by Yoshikai and coworkers f...

Scheme 12.3 Regioselectivity difference when coupling styrenes to aryl p...

Scheme 12.4 Hydroacylation of olefins with benzaldehydes reported by Bro...

Scheme 12.5 Protocols reported by Dong and coworkers for (a) hydroacylat...

Scheme 12.6 Use of [Co(PMe

3

)

4

] as a catalyst reported by Petit and cowor...

Scheme 12.7 (a) Switchable cyclization for the synthesis of quinolines a...

Scheme 12.8 Use of diazo compounds as coupling partners for the synthesi...

Scheme 12.9 Functionalization of 8‐methylquinoline with (a) alkynes and ...

Scheme 12.10 Selected examples of products achieved utilizing the 8‐amin...

Scheme 12.11 Synthesis and reactivity of organometallic aryl–Co(III) com...

Scheme 12.12 Cobalt‐catalyzed C(sp

2

)–C(sp

2

) cross‐coupling using Grignar...

Scheme 12.13 Cobalt‐catalyzed C(sp

2

)–C(sp

3

) cross‐coupling using Grignar...

Scheme 12.14 Cobalt‐catalyzed C(sp

3

)–C(sp

2

) cross‐coupling using (a) alk...

Scheme 12.15 Cobalt‐catalyzed C(sp

3

)–C(sp

2

) cross‐coupling using benzyl ...

Scheme 12.16 Cobalt‐catalyzed C(sp

3

)–C(sp

2

) Heck‐type coupling described...

Scheme 12.17 Cobalt‐catalyzed C(sp)–C cross‐couplings using alkynyl hali...

Scheme 12.18 Cobalt‐catalyzed C(sp

2

)–C(sp

2

) cross‐couplings using aryl h...

Scheme 12.19 Cobalt‐catalyzed C(sp

2

)–C(sp

2

) cross‐couplings using two di...

Scheme 12.20 Cobalt‐catalyzed amination using (a) pyridine oxide (PyO) [...

Scheme 12.21 Cobalt‐catalyzed CH bond nitration reactions reported by (...

Scheme 12.22 Preparation of β‐lactams (right) and β‐amido products (left...

Scheme 12.23 Cp*Co(III)‐catalyzed sulfamidation and phosphoramidation of...

Scheme 12.24 Cp*Co(III)‐catalyzed amidation of C(sp

2

)H bonds using diox...

Scheme 12.25 Co(III)/Cu(II)‐catalyzed synthesis of 1

H

‐indazoles reported...

Scheme 12.26 Niu and Song's alkoxylation of aromatic and olefinic substr...

Scheme 12.27 Cp*Co(III)‐catalyzed CS bond formation reactions reported ...

Scheme 12.28 Cp*Co(III)‐catalyzed halogenation and cyanation of CH bond...

Scheme 12.29 Cobalt‐catalyzed C–S formation disclosed by (a) Cheng and c...

Scheme 12.30 Cobalt‐catalyzed C(sp

2

)–N cross‐couplings reported by (a) T...

Scheme 12.31 Cobalt‐catalyzed C(sp

2

)–O cross‐couplings with phenols [121...

Scheme 12.32 Photocatalyzed formation of (a) C(sp

3

)–C(sp

2

) by Wu et al. ...

Chapter 13

Scheme 13.1 Trifluoromethylation of aryl iodides.

Scheme 13.2 Mechanism for the copper‐mediated trifluoromethylation invol...

Scheme 13.3 Copper‐catalyzed trifluoromethylation with (trifluoromethyl)...

Scheme 13.4 Copper‐catalyzed trifluoromethylation of diazonium salts.

Scheme 13.5 Copper‐mediated oxidative trifluoromethylation of alkynes.

Scheme 13.6 Copper‐catalyzed trifluoromethylation of heteroaromatics.

Scheme 13.7 Copper‐catalyzed trifluoromethylation of boronic derivatives...

Scheme 13.8 Copper‐catalyzed radical trifluoromethylation.

Scheme 13.9 Mechanisms for copper‐catalyzed radical trifluoromethylation...

Scheme 13.10 Possible reaction pathways for activation of Umemoto's reag...

Scheme 13.11 Electrophilic trifluoromethylation of silyl enol ethers and...

Scheme 13.12 Electrophilic trifluoromethylation of hydrazones.

Scheme 13.13 Copper‐catalyzed allylic trifluoromethylation of unactivate...

Scheme 13.14 Copper‐catalyzed allylic trifluoromethylation of allyl sila...

Scheme 13.15 Copper‐catalyzed trifluoromethylation of alkenes with nucle...

Scheme 13.16 Copper‐catalyzed radical trifluoromethylation/aryl migratio...

Scheme 13.17 Copper‐catalyzed trifluoromethylchlorosulfonylation of alke...

Scheme 13.18 Radical trifluoromethylation by photoactivatable copper com...

Scheme 13.19 Radical trifluoromethylation with copper complex bearing re...

Scheme 13.20 Copper‐catalyzed nucleophilic trifluoromethylthiolation of ...

Scheme 13.21 Copper‐catalyzed nucleophilic trifluoromethylthiolation of ...

Scheme 13.22 Copper‐catalyzed nucleophilic trifluoromethylthiolation wit...

Scheme 13.23 Copper‐catalyzed nucleophilic trifluoromethylthiolation wit...

Scheme 13.24 Copper‐catalyzed nucleophilic trifluoromethylthiolation of ...

Scheme 13.25 Nickel‐catalyzed nucleophilic trifluoromethylthiolation of ...

Scheme 13.26 Nickel‐catalyzed nucleophilic trifluoromethylthiolation of ...

Scheme 13.27 Revised structure for dimethyl‐trifluoromethylsulfanyl‐benz...

Scheme 13.28 Copper‐based catalytic systems for electrophilic trifluorom...

Scheme 13.29 Copper‐catalyzed trifluoromethylthiolation of boronic acids...

Scheme 13.30 An alternative SCF

3

source for copper‐catalyzed electrophil...

Scheme 13.31 Cu(I)‐catalyzed perfluoroalkylation of aryliodides with 1

H

‐...

Scheme 13.32 Cu(I)‐catalyzed perfluoroalkylation of aryliodides using zi...

Scheme 13.33 Cu(I)‐catalyzed perfluoroalkylthiolation of alkynes using p...

Chapter 14

Scheme 14.1 Oxidation of C



C and CH bonds.

Figure 14.1 Structure of the (salen)Mn catalysts

1a‐h

used by Koc...

Figure 14.2 Chiral Mn–salen complexes

2

–

5

used for the asymmetric epoxid...

Figure 14.3 The mep and mcp ligands and the corresponding Mn complexes

6

Scheme 14.2 Epoxidation of olefins with the Mn/2‐PyCO

2

H catalyst system....

Figure 14.4 Mn catalysts used for olefin epoxidation by

Figure 14.5 Ligands and complexes reported by Sun et al. for the (enanti...

Scheme 14.3 Dinuclear Mn complexes explored by Feringa for olefin cis‐di...

Scheme 14.4 (Enantioselective) cis‐hydroxylations reported by Feringa an...

Figure 14.6 Ligand used by Que and Valentine to generate Fe‐based epoxid...

Scheme 14.5 Fe‐based epoxidation catalyst developed by Beller (left) and...

Figure 14.7 Mep‐ and mcp‐based iron epoxidation catalysts reported by Ja...

Figure 14.8 Fe‐based epoxidation catalysts developed by Sun.

Scheme 14.6 Bulky, C

1

‐symmetric catalyst

22

developed by Costas and Klei...

Figure 14.9 Fe complexes studied by Que et al. in olefin oxidations.

Figure 14.10 Ligands studied by Che et al. for Fe‐catalyzed olefin dihyd...

Figure 14.11 Alternative ligand topologies used for Fe‐catalyzed olefin ...

Figure 14.12 Cobalt‐based catalysts for the oxidation of olefins.

Figure 14.13 1,3‐Diketone‐type ligands used in Ni‐catalyzed aerobic epox...

Figure 14.14 Ni catalysts used for the aerobic epoxidation of olefins (T...

Figure 14.15 Ligand systems based on the PY2 chelating moiety used by Va...

Figure 14.16 Sugar‐derived ligand (top) and Cu‐based epoxidation catalys...

Scheme 14.7 Selective Mn‐catalyzed CH oxidations reported by Bryliakov....

Scheme 14.8 Predictable and selective aliphatic CH oxidation reported b...

Scheme 14.9 Selective CH oxidation reported by Kodera et al.

Scheme 14.10 Methylene oxidation by [Fe(PDP)(CF

3

SO

3

)

2

] (

42

) and [Fe(mcp)...

Scheme 14.11 Regioselective oxidation of

trans

‐androsterone acetate gove...

Figure 14.17 Ligands used for catalytic alkane oxidations with cobalt.

Figure 14.18 Ligands used by Itoh for Ni‐catalyzed CH oxidations.

Figure 14.19 Ligands used by Palaniandavar and Hikichi in CH oxidations...

Figure 14.20 Mononuclear copper complexes used in catalytic alkane oxida...

Chapter 15

Scheme 15.1 Chelation‐assisted CH functionalization.

Scheme 15.2 Hydroarylation of alkenes.

Scheme 15.3 Hydroarylation of alkynes.

Scheme 15.4 Cobalt‐catalyzed C−H activation with addition to imines.

Scheme 15.5 C−H functionalization by addition to aldehydes

24

.

Scheme 15.6 Organometallic C−H functionalization through addition to iso...

Scheme 15.7 Cobalt‐catalyzed C–H alkenylation.

Scheme 15.8 Chelation‐assisted C–H allylation.

Scheme 15.9 Chelation‐guided C–H functionalization and annulation with a...

Scheme 15.10 Synthesis of isoquinoline derivatives via C−H activation.

Scheme 15.11 Chelation‐assisted C−H functionalization of aromatic amides...

Scheme 15.12 Synthesis of indoles by organometallic C−H functionalizatio...

Scheme 15.13 Directed C−H alkynylation of (hetero)arenes.

Scheme 15.14 Cobalt‐catalyzed C−H cyanation.

Scheme 15.15 Cobalt‐catalyzed C−H arylation.

Scheme 15.16 Iron‐catalyzed C−H arylation.

Scheme 15.17 Copper‐mediated/catalyzed C−H arylation.

Scheme 15.18 Nickel‐catalyzed chelation‐assisted C−H arylation.

Scheme 15.19 Cobalt‐catalyzed C−H alkylation.

Scheme 15.20 Iron‐catalyzed C−H alkylation.

Scheme 15.21 Chelation‐assisted nickel‐catalyzed C−H alkylation.

Scheme 15.22 Chelation‐assisted C−H amination using amines.

Scheme 15.23 Chelation‐assisted C−H amination with functionalized amine ...

Scheme 15.24 Chelation‐controlled CO bond formation via CH activation....

Scheme 15.25 Chelation‐controlled C−H halogenation.

Scheme 15.26 Chelation‐assisted C−H chalcogenation.

Chapter 16

Scheme 16.1 Selected standard reduction potentials for the water electro...

Figure 16.1 Possible mechanism of O



O bond formation in the OEC...

Scheme 16.2 Schematic light‐driven water oxidation mechanism. SO stands ...

Figure 16.2 Time line with the most emblematic first‐row transition meta...

Scheme 16.3 Proposed structural rearrangement of the L

6

Mn

4

O

4

cluster dur...

Figure 16.3 [Mn

3

CaO

4

]

6+

models described by T. Agapie and coworkers....

Scheme 16.4 Mechanism proposed for the oxidation of water with [Mn

2

(μ‐O)

Scheme 16.5 (Left) Schematic diagram of dimeric Mn–porphyrin complexes t...

Figure 16.4 (a) Line drawing of the first homogeneous Mn‐WOC working wit...

Scheme 16.6 Schematic representation of the Fe–TAML, biuret Fe–

b

TAML, an...

Scheme 16.7 Differentiation between active (a) and nonactive (b) structu...

Scheme 16.8 Mechanism postulated for water oxidation with iron complexes...

Figure 16.5 Polypyridyl, polypyridylamino, and polyamine cobalt complexe...

Scheme 16.9 Mechanism of electrocatalytic water oxidation proposed for [...

Scheme 16.10 Ni complexes employed as water oxidation catalysts.

Scheme 16.11 Schematic representation of Cu‐WOCs, [(

X

bpy)Cu(μ‐OH)]

2

2+

...

Figure 16.6 (a) Schematic diagram of the mono‐copper complexes with tetr...

Chapter 17

Scheme 17.1 Carbon‐ and BN‐based hydrogen storage cycles.

Figure 17.1 State‐of‐the‐art catalysts applied in hydrogenation and deh...

Scheme 17.2 Thermodynamic data for the dehydrogenation reaction of selec...

Scheme 17.3 Sequence of events defining the acceptorless dehydrogenation...

Scheme 17.4 Schematic representation of the two general mechanisms, inne...

Figure 17.2 Iron‐based catalysts promoting the acceptorless dehydrogenat...

Scheme 17.5 Dehydrogenation of formic acid promoted by catalyst

18

gener...

Scheme 17.6 Proposed catalytic cycles for the dehydrogenation of formic ...

Scheme 17.7 Dehydrogenation of formic acid promoted by catalyst

24

gener...

Scheme 17.8 Dehydrogenation of formic acid/triethylamine adduct promoted...

Scheme 17.9 Dehydrogenation of formic acid promoted by catalyst

29

and t...

Scheme 17.10 Dehydrogenation of formic acid/amine adducts promoted by Ni...

Scheme 17.11 Dehydrogenation of TEAF promoted by aluminum catalyst

35

: g...

Scheme 17.12 Three‐step aqueous‐phase reforming of MeOH to hydrogen and ...

Figure 17.3 Fe‐based catalysts applied in the dehydrogenation of MeOH wa...

Scheme 17.13 Dehydrogenative coupling of 1,4‐butanediol to γ‐butyrolacto...

Scheme 17.14 Cobalt‐catalyzed dehydrogenative coupling of primary alcoho...

Figure 17.4 Co‐based catalysts applied in the acceptorless dehydrogenati...

Scheme 17.15 Iron‐catalyzed dehydrogenation of 2‐pyridylmethanol derivat...

Scheme 17.16 Dehydrogenative coupling of diols and transfer hydrogenatio...

Scheme 17.17 Dehydrogenation of glycerol to lactic acid catalyzed by Fe‐...

Figure 17.5 Exemplary liquid organic hydrogen carrier systems (LOHC).

Scheme 17.18 Dehydrogenation of 1,2,3,4‐tetrahydroquinaldines by iron ca...

Figure 17.6 Selection of proposed products after dehydrogenation of ammo...

Figure 17.7 State‐of‐the‐art non‐noble metal catalysts applied in ammoni...

Chapter 18

Scheme 18.1 Proposed simplified catalytic cycle with the H‐cluster of [F...

Scheme 18.2 Catalytic proton reduction mechanism with [Fe

2

(CO)

2

(κ

2

‐dppv)

Scheme 18.3 Proposed mechanism for [Fe

2

(CO)

2

(Fc′)(κ

2

‐dppv)(μ‐adt

Bn

)] (

2

)...

Scheme 18.4 Mechanism for HER activity of a redox‐active phosphole‐based...

Figure 18.1 Selected examples of di‐iron complexes having HER activity ...

Figure 18.2 Monometallic hangman porphyrin and polypyridyl Fe

III

complex...

Figure 18.3 Examples of monoiron complexes with a dithiolate ligand.

Figure 18.4 Selected examples of cyclopentadienyl monoiron complexes.

Figure 18.5 Diglyoxime and chlatrochelate mononuclear Fe

II

systems.

Figure 18.6 Quasi linear tetra‐ and tri‐iron complexes.

Figure 18.7 Bent tri‐iron complexes.

Figure 18.8 Nitride‐ and carbide‐centered tetrairon clusters.

Scheme 18.5 Proposed H

+

/H

2

conversion at the active site of [NiFe] h...

Figure 18.9 Bioinspired [NiFe] complexes with a {Cp′FeCO} moiety.

Figure 18.10 Bioinspired [NiFe] complexes with a {Fe(CO)

3

} moiety.

Figure 18.11 Selected examples of heterobimetallic [NiFe] complexes with...

Figure 18.12 Heterobimetallic [NiFe] clusters.

Figure 18.13 Heterobimetallic [NiMn] complexes.

Figure 18.14 Tetraazamacrocycle and amine‐functionalized diphosphine Ni

I

...

Figure 18.15 Selected examples of mononuclear Ni‐based complexes with va...

Figure 18.16 Selected examples of Co‐based mononuclear complexes.

Figure 18.17 Examples of dicobalt complexes.

Scheme 18.6 Proposed mechanism of H

+

/H

2

conversion for dicobalt(III)...

Figure 18.18 Other bi‐ and polymetallic cobalt complexes.

Figure 18.19 Mn‐based mononuclear catalysts.

Figure 18.20 Examples of dimanganese complexes.

Figure 18.21 Examples of recent Cu‐based HER catalysts.

Figure 18.22 Selected examples of Mo‐based HER catalysts.

Figure 18.23 Molybdenum–polypyridyl complexes.

Figure 18.24 A dimolybdenum‐based HER catalyst.

Figure 18.25 Examples of [NiMo] and [NiW] heterobimetallic complexes.

Chapter 19

Figure 19.1 The cobalt–salen catalyst reported by Coates and coworkers ...

Figure 19.2 A cobalt–salen catalyst (

2

) reported by Darensbourg and Monc...

Figure 19.3 Bifunctional Co–salens

3

and

4

reported by Nozaki and cowork...

Figure 19.4 Bifunctional Co(salen) complexes reported by Lee and coworke...

Figure 19.5 Bifunctional Co–salens developed by Lu, Darensbourg et al. [...

Figure 19.6 Bifunctional Co–salen complexes

12

with pendant imidazolium ...

Figure 19.7 Dinuclear Co–salen complexes

14

investigated by Lu and cowor...

Figure 19.8 General structure of (substituted) Co–TPPs with ortho‐ and p...

Figure 19.9 N

4

‐ligated Co complexes

17

reported by Zevaco and coworkers ...

Figure 19.10 Macrocyclic, bifunctional bimetallic complexes

19

–

21

develo...

Figure 19.11 Co(II)/Co(III) complexes

22

and

23

used by Kerton and cowor...

Chapter 20

Figure 20.1 Selected dinitrogen reduction catalysts, their N

2

ligand IR...

Figure 20.2 The Haber–Bosch process (top) and its mechanism (bottom).

Figure 20.3 Dimeric β‐diketiminate N

2

complexes of iron (1), cobalt (2),...

Figure 20.4 Triiron β‐diketiminate N

2

complexes that split the dinitroge...

Figure 20.5 Rigid triiron β‐diketiminate complex and its subsequent redu...

Figure 20.6 Overall reaction scheme for nitrogen reduction by nitrogenas...

Figure 20.7 Two possible pathways of dinitrogen reduction to ammonia: al...

Figure 20.8 The Leigh cycle.

Figure 20.9 Thiolate‐containing iron complexes capable of binding of din...

Figure 20.10 Sulfur‐containing diiron complex that coordinates dinitroge...

Figure 20.11 Iron dinitrogen complex with a ligand featuring only thiola...

Figure 20.12 Selected nitrogen reduction molybdenum catalysts.

Figure 20.13 Reactivity of (SiP

R

3

)Fe(N

2

) complexes in the reduction of...

Figure 20.14 Mechanistic investigations on the (SiP

i

‐Pr

3

)Fe(N

2

)...

Figure 20.15 Reactivity of the (BP

i

‐Pr

3

)FeN

2

(31) complex with ...

Figure 20.16 Stepwise addition of silicon electrophiles to [(BP

i‐Pr

...

Figure 20.17 Possible mechanisms of reduction of N

2

to NH

3

using [(BP

i‐

...

Figure 20.18 Ammonia formation catalyzed by [(BP

i

‐Pr

3

)Co(N

2

)][N...

Figure 20.19 Catalysis with (CP

i

Pr

3

)Fe(N

2

)

−

(

38

) forming up to ...

Figure 20.20 Formation of ammonia with (PNP)MN

2

complex

40

(M = Fe) and

Figure 20.21 Ammonia formation by (CAAC)

2

Fe (44) and isolation of some r...

Figure 20.22 Catalytic formation of hydrazine by [Fe

0

(depe)

2

(N

2

)] (

49

). ...

Figure 20.23 Selected molybdenum catalysts that are active in the reduct...

Figure 20.24 Iron based precatalysts for silylation of dinitrogen.

Figure 20.25 Proposed catalytic cycle for the iron‐mediated silylation o...

Figure 20.26 Proposed catalytic cycle for silylation of dinitrogen using...

Figure 20.27 Cobalt‐based precatalyst systems for dinitrogen silylation ...

Figure 20.28 Proposed catalytic cycle for silylation of dinitrogen using...

Guide

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Non-Noble Metal Catalysis

Molecular Approaches and Reactions

Edited byRobertus J. M. Klein GebbinkMarc-Etienne Moret

Copyright

Editors

Prof. Dr. Robertus J. M. Klein Gebbink

Organic Chemistry & Catalysis

Debye Institute for Nanomaterials Science

Utrecht University

Universiteitsweg 99

3584 CG Utrecht

Netherlands

Dr. Marc‐Etienne Moret

Organic Chemistry & Catalysis

Debye Institute for Nanomaterials Science

Utrecht University

Universiteitsweg 99

3584 CG Utrecht

Netherlands

Cover Image: © julie deshaies/Shutterstock

All books published by Wiley‐VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

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Print ISBN: 978‐3‐527‐34061‐3

ePDF ISBN: 978‐3‐527‐69911‐7

ePub ISBN: 978‐3‐527‐69910‐0

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Preface

Since its early development in the 1960s, the field of homogeneous catalysis has led to a plethora of industrially applied organometallic catalysts and, not the least, to an in‐depth fundamental understanding of the reactivity of transition metal complexes. The threefold awarding of the Nobel Prize to the field of homogeneous catalysis in the very beginning of the twenty‐first century highlights the impact the homogeneous catalysis field has made on chemistry and synthesis in general [1–3]. Remarkably, the reactions for which these awards have been given predominantly make use of noble, platinum group metals. This illustrates the historical importance and dominance of the use of noble metals in the field of homogeneous catalysis at large, from gram‐scale, exploratory organic synthesis in pharmaceutical labs to large‐scale industrial processes.

Although non‐noble metals such as iron have been investigated from the early days of catalysis on, their noble counterparts have quickly and durably come to occupy the center of the stage. However, many recent endeavors in the field shift the focus back to non‐noble metals, sometimes referred to as “base metals,” in the development of new homogeneous catalysts. This move is largely driven by economic and environmental considerations. Not only are market prices of noble metals generally high, which is largely due to their relatively low abundancy in the earth crust, but these prices are often rather volatile as well. In addition, many of the noble metals are associated with toxicity issues for humans and the environment. As a consequence, the use of noble metal catalysts in, e.g., later stages of active pharmaceutical ingredient synthesis requires stringent purification procedures with the associated energetic and financial costs.

Motivated by many of these considerations, the scientific community has become interested in the study and development of homogeneous catalysts that are based on non‐noble metals. The practical use of metals such as manganese, iron, and cobalt promises to alleviate, at least partly, some of these issues. A recent analysis by the EU on the criticality of raw materials furthermore shows that the late first‐row transition metals are all above the economic importance threshold, whereas all except cobalt are below the supply risk threshold [4] . This is in contrast with many other raw materials, including the platinum group metals, where geopolitical issues come in to play as well.

One should not forget, though, that the current blossoming of the field of non‐noble metal catalysis is for a large part simply born out of scientific curiosity. The availability of multiple oxidation states, often spaced by one‐electron differences, and the strong tendency to adopt high‐spin electron configurations lead to markedly different chemistry for non‐noble metals with respect to noble metals, e.g. in terms of kinetic lability and lifetimes of intermediates. The investigation of non‐noble metals in homogeneous catalysis is therefore expected to unravel fundamentally new reactivity patterns, leading to new catalysts, and, not unimportantly, to new applications. In contrast to the early days of catalysis, the current availability of advanced spectroscopic and analytical tools, including density functional theory and other computational methods, now allows for a detailed characterization and understanding of non‐noble metal complexes, catalysts, and reactive intermediates. This situation is clearly different from the times when Kochi was exploring iron‐mediated CC coupling chemistry in the 1940s (see Chapter by Neidig et al.).

Although the terms “non‐noble metals” and “base metals” are broadly defined, we opted to focus this book on the late, first‐row transition metals Mn, Fe, Co, Ni, and Cu, given the volume of recent interest in and the development of the catalytic chemistry of these metals. Only in selected cases will examples using other metals be discussed, and if so mainly to put recent developments in perspective. In this sense, the book adds on and complements earlier books on related topics, such as the book edited by Bullock on “catalysis without precious metals” [5] .

The first four chapters of the book deal with conceptual aspects of non‐noble metal catalysis in order to provide the reader with some further background. These chapters include discussions on non‐innocent ligands (de Bruin, Chapter ), computational methods (Ye, Neese, Chapter ), multinuclear complexes (Mankad, Chapter ), and industrial applications (Alsters, Le Fort, Chapter ). Subsequent chapters discuss typical reaction classes, such as additions to CC , CN, and CO double bonds (Chapters 6, 7, 8, 9, 10), the formation of CC and Chetero atom bonds through cross‐coupling (Chapters 11, 12, 13), (formal) oxidation reactions (Chapters 14, 15, 16), and small‐molecule activation (Chapters 16, 17, 18, 19, 20). These reaction classes are chosen to be representative of the broad range of reactions for which non‐noble metal catalysts are being investigated. These chapters are presented from the point of view of synthetic method development or of catalyst development and may focus on the use of a single metal for a particular reaction or on a particular reaction itself. Accordingly, a particular reaction or catalyst may appear in more than one chapter.

We hope this book provides the more experienced reader with a contemporary overview of the current standing in the field of homogeneous non‐noble metal catalysis and appeals to the less experienced reader in raising further interest in the field.

A big “thank you” not only goes out to all the contributors to this book, who have kept up with us as editors, but also the support staff at Wiley for their help and patience. We would also like to thank our collaborators within the European training network NoNoMeCat on homogeneous “non‐noble metal catalysis” for the joint and stimulating efforts in further developing the field and training the next general generation of researchers in the field [6] . Not surprisingly, many of these collaborators are contributors to this book.

Utrecht, July 2018 Robertus J. M. Klein Gebbink

Marc‐Etienne Moret

References

1 The Nobel Prize in Chemistry 2001 was awarded to William S. Knowles and Ryoji Noyori “for their work on chirally catalyzed hydrogenation reactions” and to K. Barry Sharpless “for his work on chirally catalyzed oxidation reactions.” See:

www.nobelprize.org/nobel_prizes/chemistry/laureates/2001/

.

2 The Nobel Prize in Chemistry 2005 was awarded to Yves Chauvin, Robert H. Grubbs, and Richard R. Schrock “for the development of the metathesis method in organic synthesis.” See:

www.nobelprize.org/nobel_prizes/chemistry/laureates/2005/

.

3 The Nobel Prize in Chemistry 2010 was awarded jointly to Richard F. Heck, Ei‐ichi Negishi, and Akira Suzuki “for palladium‐catalyzed cross couplings in organic synthesis.” See:

www.nobelprize.org/nobel_prizes/chemistry/laureates/2010/

.

4 European Commission. Study on the review of the list of Critical Raw Materials.

https://publications.europa.eu/en/publication-detail/-/publication/08fdab5f-9766-11e7-b92d-01aa75ed71a1/language-en

(accessed 19 July 2018).

5 Bullock, R.M. (ed.) (2010).

Catalysis without Precious Metals

. Wiley.

6 For information on the NoNoMeCat network see:

www.nonomecat.eu

(accessed 17 July 2018).

1Application of Stimuli‐Responsive and “Non‐innocent” Ligands in Base Metal Catalysis

Andrei Chirila Braja Gopal Das Petrus F. Kuijpers Vivek Sinha and Bas de Bruin

University of Amsterdam (UvA), Van 't Hof Institute for Molecular Sciences (HIMS), Homogeneous, Supramolecular and Bio‐Inspired Catalysis (HomKat), Science Park 904, 1098 XH Amsterdam, The Netherlands

1.1 Introduction

The development of efficient and selective catalysts is an important goal of modern research in chemistry – the science of matter and its transformations. Our society needs new catalysts to become more sustainable, and a desire for selectivity and efficiency in the preparation of medicines and materials has boosted our interest in developing new methods based on homogeneous catalysis, particularly on the development of new ligands that can be fine‐tuned to specific needs. The properties of a metal complex as a whole are the result of the interaction between the metal center and its surrounding ligands. In traditional approaches, the steric and electronic properties of the spectator ligand are used to control the performance of the catalyst, but most of the reactivity takes place at the metal. Recent new approaches deviate from this concept and make use of ligands that play a more prominent role in the elementary bond activation steps in a catalytic cycle [1, 2]. The central idea is that the metal and the ligand can act in a synergistic manner to facilitate a chemical process. In this light, complexes based on the so‐called “non‐innocent” ligands offer interesting prospects and have attracted quite some attention.

The term “non‐innocent” is broadly used, and diverse authors give different interpretations to the term. It was originally introduced by Jørgensen [3] to indicate that assigning metal oxidation states can be ambiguous when complexes contain redox‐active ligands. As such, ligands that get reduced or oxidized in a redox process of a transition metal complex are often referred to as “redox non‐innocent.” [4, 5] With modern spectroscopic techniques, combined with computational studies, assigning metal and ligand oxidations states has become less ambiguous, and hence, many authors started to use the term “redox‐active ligands” instead. Gradually, many authors also started to use the term “non‐innocent” for ligands that are more than just an ancillary ligand, frequently involving ligands that have reactive moieties that can act in cooperative (catalytic) chemical transformations, act as temporary electron reservoirs, or respond to external triggers to modify the properties or reactivity of a complex. A common objective of many of these investigations is to achieve better control over the catalytic reactivity of first‐row transition metal complexes, with the ultimate goal to replace the scarce, expensive noble metals currently used in a variety of catalytic processes by cheap and abundant first‐row transition metals. Instead of providing a comprehensive overview of redox non‐innocent [6, 7] and cooperative ligands [1, 8, 9], this chapter is intended to provide a conceptual introduction into the topic of achieving control over the catalytic reactivity of non‐noble metals using non‐innocent ligands on the basis of recent examples.

Noble metals are frequently used in several catalytic synthetic methodologies and many industrial processes [10]. Their catalytic reactivity is most frequently based on their well‐established “two‐electron reactivity,” involving typical elementary steps such as reductive elimination and oxidative addition. These elementary steps easily occur for late (mostly second and third rows) transition metals having two stable oxidation states differing by two electrons. However, most noble metals are scarce and are therefore expensive (and sometimes toxic [11]). Therefore, it is necessary to reinvestigate the use of cheaper, abundant, and benign metals to arrive at cost‐effective alternatives. This is not an easy task, as base metals (Fe, Co, Cu, Ni, etc.) often favor one‐electron redox processes, and typical elementary steps commonly observed in noble metal catalysis are only scarcely observed for base metals. As such, the unique properties of non‐innocent ligands are advantageous to gain better control over the reactivity of base metals. In some cases, this leads to reactivity comparable to that of noble metal complexes (but more cost‐effective and benign), whereas in other cases, the combination of a base metal with a “non‐innocent” ligand can actually give access to unique new types of reactivity.

This chapter has four parts. In Section 1.2, the concept of responsive ligands is discussed, giving examples of a series of ligands that can be tuned using external stimuli such as light, pH, or ligand‐based redox reactions. These can trigger a change in the properties of the ligand, thereby modifying the reactivity of the metal. Section 1.3