PREPARATION, PROPERTIES, AND REACTIONS OF METAL-CONTAINING HETEROCYCLES .96. MONONUCLEAR, DINUCLEAR AND TRINUCLEAR METALLACYCLOALKANES OF THE IRON-TRIAD

The reaction of the bis(triflates) [F3CSO3-(CH2)(m)-O3SCF3] [m = 5-10, 12, 14, 16 (1a-i)] with Na-2[Os(CO)(4)] in dimethyl ether affords the osmacycloalkanes 2a, 2b and 2f-i (m = 5, 6, 10, 12, 14, 16), diosmacy cloalkanes 3a-i (m = 5-10, 12, 14, 16), and triosmacycloalkanes 4a-i ( m = 5-10, 12, 14 16). The structure of 3f was investigated by an X-ray structural analysis. This 22-membered diosmacycle crystallizes in the space group <P(1)over bar> with Z = 1. If the unsaturated cis-4-octen -1,8-diyl bis(trifluoromethanesulfonate) (5) is treated with Na-2[Os(C O)(4)] the diosmacyclooctadeca-5,14-diene 6 is obtained. By treating t he bis(triflates) 1a, d with Na-2[Fe(CO)(4)] the corresponding ferracy cloalkanes are formed only in situ. Insertion of carbon monoxide into the M-C a bonds leads to the cyclic ketones 7a, d and to the diketone 8d.