ORTHOMETALLATION REACTIONS OF TRIS(P-METHOXYPHENYL)PHOSPHINE WITH DIRHODIUM(II) TETRAACETATE

Reactions of dirhodium(II)tetraacetate [Rh-2(OAc)(4)] with tris(p-meth oxyphenyl)phosphine (PMP) at 1:1 and 1:2 molar ratios yield, first app ropriate adducts: [Rh-2(OAc)(4)P(p- CH3OC6H4)(3)] (1a) and [Rh-2(OAc)( 4){P(p-CH3OC6H4)(3)}(2)] (2a), and then orthometallated [Rh-2(OAc)(3){ mu-(p- CH3OC6H3)P(p-CH3OC6H4)(2)}(HOAc)(2)] (1) and [Rh-2(OAc)(2){mu-( p-CH3OC6H3)P(p-CH3OC6- H-4)(2)}(2)(HOAc)(2)] (2) complexes, respective ly. They have been characterized by spectroscopic methods. The molecul ar structure of 1 has been determined by the X-ray methods. Crystal da ta: space group P (1) over bar, a = 11.085(5), b = 11.387(5), c = 13.9 00(6) Angstrom, alpha = 97.29(3), beta = 15.23(3), gamma = 91.93(3)deg rees. In this compound The Rh-Rh distance is 2.421(1), Rh-P bond lengt h 2.196(2) and Rh-C 1.965(5) Angstrom. Lengths of bonds between rhodiu m atoms and oxygen atoms of acetato bridges are between 2.021(3) and 2 .203(3) Angstrom. (C) 1998 Elsevier Science S.A. All rights reserved.