Studies on the reactivity of the halo-hydride complexes [M(η 5-C 5H 5) 2HX] (M = Mo, W; X = Cl, Br, I)

Abstract

A convenient preparation of the cations [Mo(η 5-C 5H 5) 2HL] + and [Mo(η 5-C 5H 5) 2H(LL)] + from [Mo(η 5-C 5H 5) 2HI] ( 1), L and TlPF 6(BF 4) is described for L = CO, C 2H 4, PMe 2Ph, PEt 2,Ph, PPh 3, NH 3, NCMe and LL = Ph 2PCH 2PPh 2, (dppm), H 2NCH 2CH 2NH 2 (en). Complex 1 and butadiene give [Mo(η 5-C 5H 5) 2(η 3-CH 3C 3H 4)]BF 4. The chloro and bromo analogues of 1 are less reactive, and the W analogue of 1 does not react under the conditions used for 1. Reaction of 1 with Ph 2PCH 2CH 2PPh 2 (dppe) gives the cation [Mo(η 5-C 5H 5)(η 4-C 5H 6)dppe] + ( 18) in the presence or absence of TlPF 6. The deuterido analogue of 1, 1d gives 18d having the deuterium on the exo face of the C 5H 5D ring.