Abstract
New complexes of the type [MCp 2X(NCR)][PF 6] (M = Mo, W; X = SR, halides; R = Me, Et, Ph) have been prepared from [MCp 2X 2] and TlPF 6, NOPF 6 or [FeCp 2][PF 6], in nitrile solvents. Some reactions of these cations with nucleophiles [L] have been studied. With L = PR 3 or CO, the complexes [MCp 2(SR)L] + (R = Me, Ph) are formed. [MoCp 2(SPh)(NCMe)] + reacts with NaBH 4 to give [MoCp 2(SPh)H] and with acetone to give [MoCp 2{S(Ph)C(Me) 2O}] +. The W complexes [WCp 2X(NCR)] + add NHR′ 2 to give amidine complexes [WCp 2X{HNC(R)Nr′ 2}] + (X = SPh, Br). The mode of coordination of the nitriles to the [MoCp 2Cl] + fragment has been studied by EHMO calculations. The molecular structure of [MoCp 2I(NCMe)][PF 6] has been determined. The crystals are triclinic, space group P 1 , a 7.7989(6), b 10.3044(8), c 10.5565(5) Å, α 96.218(4), β 94.466(4), γ 102.697(5)°, V 818.21 Å 3, Z = 2. The cation has the usual bent bis-metallocene structure, and within this family of complexes is the first reported example of a complex containing a MoI bond.
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