Abstract
The reaction between benzoyl isocyanate and RhCl(Ph3P)3 afforded a complex [RhCl(Ph3P)2PhCO·NCO)]2 (1), which was converted to [(bipy)Rh(Ph3P)2(PhCO·NCO)]+BPh 4 − (2a) by bipyridine and NaBPh4. The latter complex was also obtained by the reaction of [(bipy)Rh(Ph3P)2]+ with benzoyl isocyanate. An analogous palladium complex (bipy)Pd(PhCO·NCO) (3) was prepared in the reaction of Pd2 (dibenzylideneacetone)3 with bipyridine and benzoyl isocyanate. 2-Phenylthiazoline-4,5-dione (4), a precursor of thiobenzoyl isocyanate, gave a complex RhCl(CO)(Ph3P)2 (PhCS·NCO) (5) in the reaction either with RhCl(Ph3P)3 or with RhCl(CO)(Ph3P)2. A cationic complex [(bipy)Rh(Ph3P)2(PhCS·NCO)]+BPh 4 − (6a) was also obtained. The similar reactions of Pd2(DBA)3 with 4 and bipyridine or o-phenanthroline afforded (N-N)Pd-(PhCS·NCO) complexes (7). Most of these novel complexes have a metallocyclic structure composed of M-O-C-N-C or M-S-C-N-C skeletons.
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