| Abstract
| - Upon treatment with [Me2OH][BF4] or aqueous HBF4, the isocyanide complexes trans-[Mo(CNR)(L)(Ph2PCH2CH2PPh2)2] (L = N2, nitrile, CO) generally afforded the aminocarbyne complexes, while the carbonyl complexes trans-[Mo(CO)(L‘)(Ph2PCH2CH2PPh2)2] (L‘ = N2, nitrile) gave the hydrido complexes.
- Treatment of trans-[Mo(CNPh)(N2)(dppe)2] with aqueous HBF4 afforded an aminocarbynecomplex, which was isolated as trans-[Mo(⋮CNHPh)(OCMe2)(dppe)2][BF4] (7) after crystallization of the crude product from acetone−hexane, whereas the reaction of trans-[Mo(CNBun)(N2)(dppe)2] with [Me2OH][BF4] resulted in the formation of the aminocarbenecomplex with an agostic α-C−H bond, trans-[MoF(CHNHBun)(dppe)2][BF4]. Analogoustreatment of trans-[Mo(CNR)(L)(dppe)2] (R = Ph, Bun; L = p-MeOC6H4CN, CO (4)) with[Me2OH][BF4] gave aminocarbyne complexes trans-[Mo(⋮CNHR)(NCC6H4OMe-p)(dppe)2][BF4] and cis-[Mo(⋮CNHR)(CO)(dppe)2][BF4] (10). In solution at room temperature, the lattercomplexes gradually isomerized to the hydrido complexes [MoH(CNR)(CO)(dppe)2][BF4] (12).Related aminocarbyne complexes cis-[Mo(⋮CNMeR)(CO)(dppe)2][BF4] (13) were obtainedfrom the reactions of 4 with [Me3O][BF4]. For comparison, carbonyl complexes trans-[Mo(CO)(N2)(dppe)2] and trans-[Mo(CO)(p-MeOC6H4CN)(dppe)2] were allowed to react withaqueous HBF4, which revealed the formation of the hydrido complexes [MoH(CO)(H2O)(dppe)2][BF4] (14) and [MoH(CO)(p-MeOC6H4CN)(dppe)2][BF4] (15), respectively. The X-rayanalyses were undertaken to determine the detailed structures for 7, 10a (R = Ph), 12a (R= Ph), 13b (R = Bun), 14·THF, and 15·Et2O.
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