VINYLIDENE TRANSITION-METAL COMPLEXES .10. SYNTHESIS OF ALKYNYLRHODIUM COMPLEXES CONTAINING A RHODIUM MERCURY BOND AND OF THE VINYL COMPLEX [C5H5RH(CH=CHPH)(P-I-PR3)SNCL3] FROM VINYLIDENERHODIUM PRECURSORS

The reaction of [C5H5Rh(═C═CHR)(P-i-Pr3)] (1-3) with HgCl2, HgI2, and CH3HgI in presence of triethylamine produces the alkynylrhodium complexes [C5H5RhHgX(C≡CR)(P-i-Pr3)] (4,6-11) in excellent yield. They have been characterized by1H,13C,31P, and199Hg NMR spectroscopy. Treatment of 1 (R = Ph) with SnCl2·2H2O gives the vinylrhodium compound [C5H5Rh(CH═CHPh)(P-i-Pr3)SnCl3] (12) probably via primary protonation at the metal atom. Complex 12 is also obtained from [C5H5Rh(CH═CHPh)(P-i-Pr3)Cl] and SnCl2·2H2O by insertion of tin dichloride into the Rh‒Cl bond. © 1990, American Chemical Society. All rights reserved.