PREPARATION AND MOLECULAR-STRUCTURES OF O LIGOFUNCTIONAL DIRHENIUM CARBONYL DERIVATIVES FROM DIRHENIUM NONACARBONYLPHOSPHANE

Starting with dirheniumdecacarbonyl, one CO-Ligand was eliminated oxid atively and substituted by the labile acetonitrile ligand. As an inter mediate eq-Re-2(CO)(9)NCCH3 was received. The reaction of this labilis ed carbonyl with tris(trimethylsilyl)phosphine and subsequent methanol ysis gave ax-Re-2(CO)(9)PH3, which was isolated and characterized for the first time. Photochemical and thermal reaction of ax-Re-2(CO)(9)PH 3 led to the new bi- and trinuclear complexes Re-2(mu-H)(mu-PHRe(CO)(5 ))(CO)(8), Re-2(mu-PH2)(2)(CO)(8) and Re-2(mu-H). (mu-PH2)(CO)(8), whi ch were characterized by IR-, H-1- and P-31- NMR spectroscopy. The str uctures of ax-Re-2(CO)(9)PH3, Re-2(mu-H)(mu(3)-PHRe(CO)(5))(CO)(8) and Re-2(mu-PH2)(2)(CO)(8) were confirmed by single-crystal X-ray analysi s. ax-Re-2(CO)(9)PH3 has a very short Re-P bond length of 228(2) pm.