(Cycloheptatrienyl)hydridotungsten Complexes

Abstract
Carbonyl(cycloheptatrienyl)iodo(phosphorus donor)tungstens ([WI(C7H7)(CO)L]; L = P(OMe)3, 1a; L = P[O(i‐Pr)]3, 1b; L = PPh3, 1c) were prepared from dicarbonyl(cycloheptatrienyl)iodotungsten ([WI(C7H7)(CO)2)] via a carbonyl‐substitution process. Similarly, bromocarbonyl(phosphorus donor)(1,2,4,6‐tetramethylcycloheptatrienyl)tungstens ([WBr(Me4C7H3)(CO)L]; L = P(OMe)3, 6a; L = P[O(i‐Pr)]3, 6b; L = PPh3, 6c) were obtained from the reaction of bromodicarbonyl(1,2,4,6)‐tetramethylcycloheptatrienyl)tungsten ([WBr(Me4C7H3)(CO)2]; 4) with L. The reduction of 1a‐c, 4, and 6a, b with sodiumdihydridobis(2‐methoxyethoxy)aluminium in toluene led to stable hydrido complexes [WH(R4C7H3)(CO)L] (R = H, L = P(OMe)3, 2a; R = H, L = P[O(i‐Pr)]3, 2b; R = H, L = PPh3, 2c; R = Me, L = P(OMe)3, 7a; R = Me, L = P[O(i‐Pr)]3, 7b; R = Me, L = CO, 7d). Complexes 2a and 7b were characterized by X‐ray structure analyses.

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