DIVALENT RUTHENIUM COMPLEXES CONTAINING 1,4,7-TRITHIACYCLONONANE AND CYCLOOCTA-1,5-DIENE (C8H12) OR 1-3 5,6-ETA-CYCLOOCTADIENYL (C8H11)/

The complex (eta(2),eta(2)-1,5-COD)(eta(6)-1,3,5-COT)(1)dagger reacted with 1,4,7-trithiacyclononane (9S3) in the presence of 1-2 mol equiv. of HPF6 to give a eta(2),eta(3)-cyclooctadienyl complex [Ru(1-3:5,6 e ta-C8H11)(9S3)]PF6 (3) as the main product, together with compounds co ntaining the cations [Ru(eta(2),eta(2)-1,5-COD)(9S3)(L)](2+) [L = H2O (4a), THF (4b)]. The latter are formed reversibly from 3 in the presen ce of an excess of HPF6, and are converted by acetonitrile into [Ru(et a(2),eta(2)-1,5-COD)(9S3)(NCMe)](2+) (5). The structures of 3 and of t he PF6 and PO2F2 salts of 5 have been determined by X-ray crystallogra phy. Copyright (C) 1996 Elsevier Science Ltd