Reactions of [(Me3SiNCH2CH2)3N]WH with dihydrogen, olefins, acetylenes, carbon monoxide, N-BUTYLISOCYANIDE (cas 2769-64-4) and azobenzene

Add time:07/12/2019    Source:sciencedirect.com

Dihydrogen reacts slowly with [N3N]WH ([N3N]3−[(Me3SiNCH2CH2)3N]3−) in benzene at 22°C to form white, crystalline, diamagnetic [N3N]WH3 quantitatively. [N3N]WH in C6D6 reacts with ethylene to produced [N3N]WCMe quantitatively, while the reaction between [N3N]WH and propylene at 45°C for 24 h produces a mixture of [N3N]WCCH2CH3 and [N3N]WH3. Addition of 1 equiv. of diphenylacetylene to [N3N]WH gives the diamagnetic ‘tungstacyclopropene’ complex, [N3N]W(CPhCHPh). Heating a mixture of [N3N]WH and 1 equiv. of azobenzene to 75°C produces the green azobenzene adduct, [N3N]W(H)(PhNNPh), while [N3N]WH reacts with 1 equiv. of carbon monoxide at 0°C to produce [N3N]W(H)(CO). Upon addition of trimethylamine to a mixture of [N3N]W(H)(CO) and Me3SiI, colorless [N3N]WCOTMS is formed. [N3N]WH reacts with 1 equiv. of N-BUTYLISOCYANIDE (cas 2769-64-4) at −20° to yield diamagnetic [N3N]W(H)(BuNC). The structures of [N3N]WH3, [N3N]W(PhCCHPh), [N3N]W(H)(PhNNPh) and [N3N]W(H)(CO) have been determined via X-ray crystallography.

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