Protonation and Methylation of Zerovalent Molybdenum Complexes of the Types <i>trans</i>-[Mo(CNR)(L)(Ph<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>PPh<sub>2</sub>)<sub>2</sub>] (R = Ph or Bu<i><sup>n</sup></i><sup></sup>; L = N<sub>2</sub>, CO, or Nitrile) and <i>trans</i>-[Mo(CO)(L‘)(Ph<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>PPh<sub>2</sub>)<sub>2</sub>] (L‘ = N<sub>2</sub> or Nitrile) To Give Carbyne or Hydrido Complexes<sup>1</sup>
收藏资源简介：
Treatment of trans-[Mo(CNPh)(N2)(dppe)2] with aqueous HBF4 afforded an aminocarbyne complex, 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 aminocarbene complex with an agostic α-C−H bond, trans-[MoF(CHNHBun)(dppe)2][BF4]. Analogous treatment 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 latter complexes 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 obtained from 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 with aqueous 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-ray analyses were undertaken to determine the detailed structures for 7, 10a (R = Ph), 12a (R = Ph), 13b (R = Bun), 14·THF, and 15·Et2O.
