THE REACTION BETWEEN 5-C5H5M(CO)3>2, η5-C5H5M(CO)3I (M = Mo, W) AND ISONITRILES

Article abstract of DOI:10.1016/S0022-328X(00)81006-2

The reaction between η⁵-C5H5M(CO)3I (M = Mo, W) and isonitriles, RNC, (RNC = PhCH2NC, t-BuNC and 2,6-dimethylphenylisocyanide (XyNC)) is catalysed by the dimer <η⁵-C5H5M(CO)3>2 (M = Mo, W) to yield η⁵-C5H5M(CO)(3-n)(RNC)nI (n = 1-3) and <η⁵-C5H5Mo(RNC)4>I.The complexes (η⁵-C5H5)2Mo2(CO)(6-n)(RNC)n (n = 1, RNC = MeNC, PhCH2NC, XyNC, t-BuNC; n = 2, RNC = t-BuNC) have been prepared in moderate yield from the direct reaction between <η⁵-C5H5Mo(CO)3>2 and RNC, and also catalyse the above reaction.A reaction pathway involving a fast non-chain radicalmechanism and a slower chain radical mechanism is proposed to account for the catalysed reaction.