Silylation of silylketenes

Николаева, С. Н.; Ponomarev, S. V.; Petrosyan, V. S.; Lorberth, Jörg

doi:10.1016/s0022-328x(97)00006-5

Cited by 5 publications

(3 citation statements)

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“…Warming either 13- 13 C or 14- 13 C above −60 °C under N 2 resulted in conversion of the Mo species to dinitrogen complex 5 , and the growth in of a pair of doublets in the 13 C{ 1 H} NMR spectrum (131.3 and 5.9 ppm, 1 J (C,C) = 139.6 Hz), consistent with formation of sodium silyl ethynolate, 6b (Scheme ). As reported previously, , addition of a small silyl electrophile to the trimethylsilyl ethynolate yielded disilyl ketene, 6c ( 13 C{ 1 H} δ = 167.5 and 1.1 ppm, 1 J (C,C) = 82.3 Hz), the thermodynamically preferred isomer of the disilylated C 2 O 1 product.…”

Section: Results and Discussionsupporting

confidence: 75%

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Mechanism of Molybdenum-Mediated Carbon Monoxide Deoxygenation and Coupling: Mono- and Dicarbyne Complexes Precede C–O Bond Cleavage and C–C Bond Formation

Buss

Agapie

2016

J. Am. Chem. Soc.

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Deoxygenative coupling of CO to value-added C≥2 products is challenging and mechanistically poorly understood. Herein, we report a mechanistic investigation into the reductive coupling of CO, which provides new fundamental insights into a multielectron bond-breaking and bond-making transformation. In our studies, the formation of a bis(siloxycarbyne) complex precedes C–O bond cleavage. At −78 °C, over days, C–C coupling occurs without C–O cleavage. However, upon warming to 0 °C, C–O cleavage is observed from this bis(siloxycarbyne) complex. A siloxycarbyne/CO species undergoes C–O bond cleavage at lower temperatures, indicating that monosilylation, and a more electron-rich Mo center, favors deoxygenative pathways. From the bis(siloxycarbyne), isotopic labeling experiments and kinetics are consistent with a mechanism involving unimolecular silyl loss or C–O cleavage as rate-determining steps toward carbide formation. Reduction of Mo(IV) CO adducts of carbide and silylcarbyne species allowed for the spectroscopic detection of reduced silylcarbyne/CO and mixed silylcarbyne/siloxycarbyne complexes, respectively. Upon warming, both of these silylcarbynes undergo C–C bond formation, releasing silylated C2O1 fragments and demonstrating that the multiple bonded terminal MoC moiety is an intermediate on the path to deoxygenated, C–C coupled products. The electronic structures of Mo carbide and carbyne species were investigated quantum mechanically. Overall, the present studies establish the elementary reactions steps by which CO is cleaved and coupled at a single metal site.

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Section: Results and Discussionsupporting

confidence: 75%

“…This is the thermodynamically preferred isomer of oxyacetylenes bearing small silyl substituents. 9,10 Figure S22- 13 …”

Section: Demonstration Of C-c Bond Formation and Organic Fragment Relmentioning

confidence: 99%