ORGANOMETALLIC COMPOUNDS OF RUTHENIUM CONTAINING AN ANIONIC OXYGEN TRIPOD LIGAND

Reaction of NaLOEt (L-OEt = (eta(5)-C5H5)Co{P(O)(OEt)(2)}(3)) with Ru( PPh3)(3)Cl-2, Ru(DMSO)(4)Cl-2 (DMSO = dimethyl sulfoxide), and Ru(PPh3 )(2)(CO)Cl(CH=CHPh) afforded LOEtRu(PPh3)(2)Cl (1), LOEtRu(DMSO)(2)Cl (2), and LOEtRu(PPh3)(CO)(CH=CHPh) (3), respectively. The structures o f complexes 1 and 2 have been established by X-ray crystallography. Th e mean Ru-O, Ru-P, and Ru-Cl bond distances in 1 are 2.183, 2.267, and 2.393(3) Angstrom, respectively. The mean Ru-O, Ru-S, and Ru-Cl dista nces in 2 are 2.118, 2.188, and 2.362(2) Angstrom, respectively. Treat ment of 3 with HBF4 yielded the olefin complex [LOEtRu(PPh3)(CO)(eta(2 )-PhCH=CH2)]BF4 (4). Reaction of complex 1 with PhC=CH in the presence of NH4PF6 gave the vinylidene complex [LOEtRu(PPh3)(2)(=C=CHPh)](PF6) (6). The mean Ru-O, Ru-P, and Ru-C distances in 6 are 2.127, 2.344, a nd 1.80(2) Angstrom, respectively. Deprotonation of 6 with NaOH gave t he acetylide complex LOEtRu(PPh3)(2)(C=CPh) (7). Reaction of complex 1 with 3-butyn-1-ol in the presence of NH4PF6 afforded the cyclic carbe ne complex [LOEtRu(PPh3)(2)- {=C(CH2)(3)O}]PF6 (8). The mean Ru-O, Ru- P, and Ru-C distances in 8 are 2.175, 2.335, and 1.87(1) Angstrom, res pectively. Reaction of LOEtRu(PPh3)(2)Cl with I-2 afforded the cation [LOEtRu(PPh3)(2)Cl](+) (1(+)), isolated as the I-3 and PF6 salts. The mean Ru-O, Ru-P, and Ru-Cl distances in 1(+) are 2.095, 2.380, and 2.3 00(3) Angstrom, respectively. The cyclic voltammogram of 1 in CH2Cl2 e xhibits a reversible Ru(III/II) couple at -0.021 V vs Cp2Fe+/0 .