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Nitrosyl Complexes in Homogeneous Catalysis

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Book cover Nitrosyl Complexes in Inorganic Chemistry, Biochemistry and Medicine I

Part of the book series: Structure and Bonding ((STRUCTURE,volume 153))

Abstract

In this chapter the application of transition metal nitrosyl complexes in homogeneous catalysis has been reviewed. Particular attention was paid to the function of nitrosyl as: (1) a π-accepting ancillary ligand; (2) a non-innocent ligand capable of reversible linear/bent transformations triggering catalytic reaction courses; (3) a redox-active ligand functioning as a “nitrosyl/nitro” redox couple for oxygen atom transfer reactions. The catalytic performance and the reaction mechanisms are discussed in terms of the respective function of the NO ligand. Group 6 molybdenum and tungsten mononitrosyl hydride complexes are reviewed with respect to their activity in hydrogenations proceeding with heterolytic splitting of H2. Group 7 rhenium mononitrosyl and dinitrosyl hydride complexes are reviewed with respect to their highly efficient performance in hydrogen-related catalyses, which is highlighted by alkene hydrogenations based on Re(I) mononitrosyl complexes and efficient transfer hydrogenations based on bifunctional Shvo-type Re–H/OH and Noyori-type Re–H/NH complexes. Group 8 iron mononitrosyl- and dinitrosyl-based catalysts are surveyed with respect to their function as Lewis acids inducing nucleophilic activity in Lewis acid type organic transformations. Then the “catalytic nitrosyl effect” is described boosting catalyses by reversible nitrosyl bending, which plays a crucial role in Re(−I) dinitrosyl and Re(I) mononitrosyl catalytic systems. The oxygen atom transfer reaction based on the “nitrosyl/nitro” redox couple involving the Co, Pd, Rh, and Ru metal centers was also reviewed.

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Abbreviations

BArF 4 :

B[3,5-(CF3)2C6H3]4

Cy:

Cyclohexyl

Dcype:

1,2-Bis(dicyclohexylphosphino)ethane

Dippe:

1,2-Bis-(diisopropylphosphino)ethane

Dippf:

1,1′-Bis(diisopropylphosphino)ferrocene

Dippp:

1,3-Bis(diisopropylphosphino)-propane

Diprpfc:

1,1′-Bisdiisopropylphosphinopherrocene

DMF:

Dimethylformamide

Dmpe:

1,2-Bis-(dimethylphosphino)ethane

Dpephos:

Bis(2-(diphenylphosphino)phenyl) ether

Dppfc:

1,1′-Bis(diphenylphosphino)ferrocene

DQCC:

Deuterium quadrupole coupling constants

edta:

Ethylenediaminetetraacetate

Homoxantphos:

10,11-Dihydro-4,5,-bis(diphenylphosphino)dibenzo[b,f]oxepine

IMes:

1,3-Bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene

KOtAm:

Potassium 2-methylbutan-2-olate

LA:

Lewis acid

MS:

Molecular sieves

MTBE:

Methyl tert-butyl ether

Ph:

Phenyl

Pr:

Isopropyl

Py:

Pyridine

Saloph:

N,N′-bisalicylidene-o-phenylenediamino

SIMes:

1,3-Bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene

Sixantphos:

4,6-Bis(diphenylphosphino)-10,10-dimethylphenoxasilin

TBABr:

Tetrabutylammonium bromide

TBAF:

Tetrabutylammonium fluoride

TOF:

Turn over frequency

TON:

Turn over number

TPP:

Tetraphenylporphyrin

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Acknowledgments

We are grateful to the financial support from the Swiss National Science Foundation, Lanxess AG, Leverkusen, Germany, the Funds of the University of Zurich, the DFG and SNF within the project “Forschergruppe FOR1175 – Unconventional Approaches to the Activation of Dihydrogen.”

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  1. Anorganisch-Chemisches Institut, Universität Zürich, Winterthurerstr. 190, 8037, Zurich, Switzerland

    Yanfeng Jiang & Heinz Berke

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  1. Yanfeng Jiang
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  2. Heinz Berke
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Correspondence to Heinz Berke .

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  1. Inorganic Chemistry Laboratory, University of Oxford, Oxford, United Kingdom

    D. Michael P. Mingos

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Jiang, Y., Berke, H. (2013). Nitrosyl Complexes in Homogeneous Catalysis. In: Mingos, D. (eds) Nitrosyl Complexes in Inorganic Chemistry, Biochemistry and Medicine I. Structure and Bonding, vol 153. Springer, Berlin, Heidelberg. https://doi.org/10.1007/430_2013_97

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