Hydrosilane-induced reductive coupling of carbon monoxide

Kaplan, Leonard

doi:10.1021/om00068a025

Organometallics

1982

DOI: 10.1021/om00068a025

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Hydrosilane-induced reductive coupling of carbon monoxide

Leonard Kaplan¹

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1984

2007

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Cited by 13 publications

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“…To our knowledge, this is the first example of the coupling of two carbon monoxide molecules by the reaction with hydrosilane to give an alkyne molecule. Interestingly, hydrosilane-induced reductive coupling of carbon monoxide has been reported to form 1,2-ethanedioxy groups . Furthermore, Murai et al have reported the Rh-catalyzed reductive oligomerization of CO with hydrosilanes and the Ru-catalyzed synthesis of catechols from two CO's, HSiR 3 , and 1,6-diynes, in which a dioxyacetylene−metal complex has been proposed as a key intermediate .…”

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Photochemical Reaction of CpFe(CO)₂SiMe₃ (Cp = η⁵-C₅H₅) with a Trihydrosilane Containing a Bulky Amino Substituent, Bis(trimethylsilyl)aminosilane

et al. 2007

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A photochemical reaction between CpFe(CO)2SiMe3 and (Me3Si)2NSiH3 in hexane gave the silylyne-bridged triiron complex Cp3Fe3(CO)4SiN(SiMe3)2 (2) and a diiron complex bridged by a four-membered cyclic silylene, Cp2Fe2(CO)2(μ-CO)(μ-SiN(SiMe3)2SiMe2CH2) (3). In contrast, the silylene- and alkyne-bridged triiron complex Cp3Fe3{μ2-SiHN(SiMe3)2}{μ3-COSiH2N(SiMe3)2}{μ3-η2-C2O2-SiHN(SiMe3)2} (4) was formed as the main product by a similar reaction in toluene.

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Photochemical Reaction of CpFe(CO)₂SiMe₃ (Cp = η⁵-C₅H₅) with a Trihydrosilane Containing a Bulky Amino Substituent, Bis(trimethylsilyl)aminosilane

et al. 2007

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“…The advantage of using hydrosilanes is that otherwise unstable intermediates, such as enols, can survive as a silyl derivative without isomerization to the stable keto isomer (e.g., tautomerization) at the experimental conditions used. Hydrosilanes have been used as a promoter for reductive coupling of CO to ethylene glycol from H 2 /CO 9 and used for a stoichiometirc model for the hydrogenation of CO. 5,8 To our knowledge, there has been only one report 10 on a transition-metal-catalyzed reaction of CO with a hydrosilane. We now report a novel Rh-catalyzed reductive oligomerization of CO with a hydrosilane.…”

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Reductive Oligomerization of Carbon Monoxide by Rhodium-Catalyzed Reaction with Hydrosilanes

et al. 1997

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The production of specific organic compounds via the hydrogenation of carbon monoxide represents an important pathway to row chemical material production and promises to be critically important in the coming decades, given the world situation relative to crude oil. 1,2 Extensive efforts have been made toward this goal, but the number of processes available remain limited and the mechanisms for these reactions remain unclear. 3,4 Many of the mechanisms proposed thus far are based on studies of stoichiometric reactions involving discrete isolable complexes, 4 such as acyl complexes, 5 R-oxyalkyl complexes, 6 and related materials. 7,8 Although stoichiometric approaches give useful and important information, they often deviate from actual catalytic processes. We have designed a novel catalytic reaction of CO using hydrosilanes in place of H 2 . The advantage of using hydrosilanes is that otherwise unstable intermediates, such as enols, can survive as a silyl derivative without isomerization to the stable keto isomer (e.g., tautomerization) at the experimental conditions used. Hydrosilanes have been used as a promoter for reductive coupling of CO to ethylene glycol from H 2 /CO 9 and used for a stoichiometirc model for the hydrogenation of CO. 5,8 To our knowledge, there has been only one report 10 on a transition-metal-catalyzed reaction of CO with a hydrosilane. We now report a novel Rh-catalyzed reductive oligomerization of CO with a hydrosilane. The reaction is intrinsically interesting and useful as a synthetic method. Moreover, the reaction provides an entirely novel model that may be useful for a better understanding of the mechanism of such catalytic reductions.A variety of transition-metal carbonyl complexes such as Mo-(CO) 6 , W(CO) 6 , PdCl 2 , Ru 3 (CO) 12 , RuCl 2 (PPh 3 ) 3 , Co 2 (CO) 8 , Rh 6 (CO) 16 , [RhCl(CO) 2 ] 2 , RhCl(PPh 3 ) 3 , and Ir 4 (CO) 12 have been examined for their catalytic activity with respect to reactions of CO with HSiEt 2 Me under a variety of reaction conditions (2.5 mol % of catalyst to HSiEt 2 Me, 100-180°C, CO 10-50 atm), but CO-incorporated products were not detected in GC. In most cases, the sole product obtained was MeEt 2 SiOSiEt 2 -Me. As a result of extensive examination of catalysts and additives, we have ultimately discovered that a reaction of CO with hydrosilanes can be achieved by using a Rh/amine catalytic system to give CO-incorporated products. Thus, the reaction of CO (50 atm) with HSiEt 2 Me (2.5 mmol) at 140°C in the presence of [RhCl 2 (CO) 2 ] 2 (0.05 mmol)/Et 3 N (7.5 mmol) in C 6 H 6 (5 mL) for 1 day in a 50-mL stainless steel autoclave gave MeEt 2 SiOSiEt 2 Me 11 as the main product (31% yield), along with reductive coupling of CO which gave diethylmethylsiloxymethane (1a, 2%), 1,2-bis(diethylmethylsiloxy)ethene 12 (2a, 18%, Z/E ) 93/7), and 1,2,3-tris(diethylmethylsiloxy)propene (3a, 5%, Z/E ) 10/1). In addition, products that corresponded to four and five molecules of CO were also observed by GCMS (eq 1). Yields are based on the HSiEt 2 Me charged. In...

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Nickel‐Katalysierte Reduktion von Kohlenmonoxid mit Hexamethyldisilan: eine neuartige Synthese von Siloxanen

Vollhardt

Yang

1984

Angewandte Chemie

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Hydrosilane-induced reductive coupling of carbon monoxide

Cited by 13 publications

References 1 publication

Photochemical Reaction of CpFe(CO)₂SiMe₃ (Cp = η⁵-C₅H₅) with a Trihydrosilane Containing a Bulky Amino Substituent, Bis(trimethylsilyl)aminosilane

Photochemical Reaction of CpFe(CO)₂SiMe₃ (Cp = η⁵-C₅H₅) with a Trihydrosilane Containing a Bulky Amino Substituent, Bis(trimethylsilyl)aminosilane

Reductive Oligomerization of Carbon Monoxide by Rhodium-Catalyzed Reaction with Hydrosilanes

Nickel‐Katalysierte Reduktion von Kohlenmonoxid mit Hexamethyldisilan: eine neuartige Synthese von Siloxanen

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Hydrosilane-induced reductive coupling of carbon monoxide

Cited by 13 publications

References 1 publication

Photochemical Reaction of CpFe(CO)2SiMe3 (Cp = η5-C5H5) with a Trihydrosilane Containing a Bulky Amino Substituent, Bis(trimethylsilyl)aminosilane

Photochemical Reaction of CpFe(CO)2SiMe3 (Cp = η5-C5H5) with a Trihydrosilane Containing a Bulky Amino Substituent, Bis(trimethylsilyl)aminosilane

Reductive Oligomerization of Carbon Monoxide by Rhodium-Catalyzed Reaction with Hydrosilanes

Nickel‐Katalysierte Reduktion von Kohlenmonoxid mit Hexamethyldisilan: eine neuartige Synthese von Siloxanen

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Photochemical Reaction of CpFe(CO)₂SiMe₃ (Cp = η⁵-C₅H₅) with a Trihydrosilane Containing a Bulky Amino Substituent, Bis(trimethylsilyl)aminosilane

Photochemical Reaction of CpFe(CO)₂SiMe₃ (Cp = η⁵-C₅H₅) with a Trihydrosilane Containing a Bulky Amino Substituent, Bis(trimethylsilyl)aminosilane