The complex [MoCI,(EtCN),] reacts in dichloromethane with alkaryl and triaryl tertiary phosphines to form the paramagnetic, maroon complexes trans- [MoCI,L,] ( L = tertiary phosphine). In ethanol, however, tertiary phosphines react with the ethyl cyanide complex to yield the diamagnetic oxo-complexes, mer-[MoOCI,L,], which are also obtained directly from molybdenum pentachloride and the phosphine in ethanol. These, by metathesis, give the complexesmer-[MoOX,L,] (X = I, Br, NCS, or NCO). The oxo-complexes are generally green or blue according to whether the oxygen is trans to L or X respectively. lH n.m.r. and i.r. spectra were determined for structural diagnosis.

Complexes formulated [{MoOCl,(diphos)}] (red and brown isomers), MoOCl,(diphos), [MoOCl(diphos),]+. and [MoOCl,(thf) (diphos)] (diphos = Ph,P*CH,*CH,*PPh,, thf = tetrahydrofuran) have been prepared and their structures assigned on the basis of analysis, i.r. and l H n.m.r. spectra, conductivity, and magnetic measurements. Only [MoOCl(diphos),] + forms alkoxy-complexes, [MoO(OR) (diphos),]+, with alcohols in the presence of sodium carbonate.?

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