3-Hexyne complexes of molybdenum(II) and tungsten(II) containing phosphite ligands: X-ray crystal structures of [MoI2(CO)(NCMe){P(OPh)3}(η2-EtC 2Et)], [MoI2(CO)(dppe)(η2-EtC2Et)] and [MI2(CO){P(OiPr)3}2(η 2-EtC2Et)] (M=Mo and W)

Article abstract of DOI:10.1016/S0022-328X(00)00926-8

Equimolar quantities of [MoI₂(CO)(NCMe)(η²-EtC₂Et)₂] and P(OR)₃ (R=Ph, ⁱPr) gave the 3-hexyne displaced products, [MoI₂(CO)(NCMe){P(OR)₃}(η²-EtC ₂Et)] (1) and (2), which was crystallographically characterised for R=Ph. By contrast, reaction of equimolar quantities of [WI₂(CO)(NCMe)(η²-EtC₂Et)₂] and P(OR)₃ (R=Me, ⁱPr, Ph) afforded the acetonitrile displaced products, [WI₂(CO){P(OR)₃}(η²-EtC₂Et) ₂] (3 to 5). The reactions of the mono(triphenylphosphite)molybdenum complex, [MoI₂(CO)(NCMe){P(OPh)₃}(η²-EtC ₂Et)] (1) with a series of neutral mono, bidentate and anionic dithiocarbamate ligands have been investigated to give a variety of reaction products, including [MoI₂(CO)(dppe)(η²-EtC₂Et)] (12), which has been structurally characterised. Reaction of [MI₂(CO)(NCMe)(η²-EtC₂Et)₂] with two equivalents of P(OR)₃ gave the mono(3-hexyne) complexes, [MI₂(CO){P(OR)₃}₂(η²-EtC ₂Et)] {M=Mo or W; R=Me, Et, ⁱPr, ⁿBu, Ph(for M=W only)} (15 to 23), which were crystallographically characterised for M=Mo and W, R=ⁱPr 19 and 20, respectively.