A new route to metal-halogen bond formation in metal carbonyl clusters:: crystal structure of the fluorinated cluster (μ-H)Os3(CO)10(AsPh3)F

(mu-H)Os-3(Co)(10)(EPh3)[ON(CF3)(2)] (E = P, As, Sb) and (mu-H)Os-3(CO)(11)[ON(CF3)(2)] react with HX (X = F, Cl, Br, I) to afford (CF3)(2)NOH and (mu-H)OS3(CO)(10)(EPh3) (X) or (mu-H)OS3(CO)(11)(X). The reaction of (mu-H)Os-3(CO)(10)(AsPh3)[ON(CF3)(2)] with HF gives two isomers, one of which was established from X-ray crystallography to be (mu-H)Os-3(CO)(10)(AsPh3) (F) with AsPh3 and F bonded to the same Os centre. The Os-F bond and the Os-CO bond trans to it are relatively short. (C) 1998 Elsevier Science S.A. All rights reserved.