NAPHTHYNE - OSMIUM AND RUTHENIUM CLUSTER DERIVATIVES

Reaction of the 1-naphthyl derivatives E(1-C10H7)(3) (E = P, AS) with M(3)(CO)(12) (M = RU, Os) affords the series of naphthyne complexes M(3)(CO)(8)(mu-H)(2)[mu(3)-eta(4)-(C10H7)(2)E(C10H5)] (5-8) in moderate to good yield, via double metalation of the unsubstituted aromatic ring. Metalation of the substituted aromatic ring results in one complex, Os-3(CO)(9)(mu-H)[(C10H7)(2)P-(C10H6)]. Cleavage of an As-naphthyl bond affords a low yield of the naphthyne complex Ru-4(CO)(10)(mu-CO)[mu(4)-As(C10H7)][mu(4)-C10H6] (11), in which the aryne ring is at an angle of 75 degrees to the RU(4) plane and acts as a four-electron donor, making 11 formally electron deficient. Crystals of 5 are monoclinic, with a = 25.746(1) Angstrom, b = 9.688(2) Angstrom, c = 33.521(1) Angstrom, beta = 108.647(3)degrees, Z = 8, and space group C2/c. Those of 11 are triclinic, with a 11.433(3) Angstrom, b = 14.746(2) Angstrom, c = 9.958(1) Angstrom, alpha = 96.81(1)degrees, beta = 102.34(2)degrees, gamma = 78.69(2)degrees, Z = 2, space group P ($) over bar 1. The structures were solved by the Patterson method and were refined by full-matrix least-squares procedures to R = 0.033 and 0.030 (R(w) = 0.031 and 0.028) for 5308 and 4933 reflections with I greater than or equal to 3 sigma(I), respectively.