Organometallic compounds of ruthenium containing an anionic oxygen tripod ligand

Abstract

Reaction of NaLOEt (LOEt = (η5-C5H5)Co{P(O)(OEt)2} 3) with Ru(PPh3)3Cl2, Ru(DMSO)4Cl2 (DMSO = dimethyl sulfoxide), and Ru(PPh3)2(CO)Cl(CH=CHPh) afforded LOEtRu(PPh3)2Cl (1), LOEtRu(DMSO)2Cl (2), and LOEtRu(PPh3)(CO)(CH=CHPh) (3), respectively. The structures of complexes 1 and 2 have been established by X-ray crystallography. The mean Ru-O, Ru-P, and Ru-Cl bond distances in 1 are 2.183, 2.267, and 2.393(3) Å, respectively. The mean Ru-O, Ru-S, and Ru-Cl distances in 2 are 2.118, 2.188, and 2.362(2) Å, respectively. Treatment of 3 with HBF4 yielded the olefin complex [LOEtRu(PPh3)(CO)(η2-PhCH=CH 2)]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, and 1.80(2) Å, respectively. Deprotonation of 6 with NaOH gave the 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 carbene complex [LOEtRu(PPh3)2-{=C(CH2) 3O}]PF6 (8). The mean Ru-O, Ru-P, and Ru-C distances in 8 are 2.175, 2.335, and 1.87(1) Å, respectively. Reaction of LOEtRu(PPh3)2Cl with I2 afforded the cation [LOEt-Ru(PPh3)2Cl]+ (I+), isolated as the I3 and PF6 salts. The mean Ru-O, Ru-P, and Ru-Cl distances in 1+ are 2.095, 2.380, and 2.300(3) Å, respectively. The cyclic voltammogram of 1 in CH2Cl2 exhibits a reversible Ru(III/II) couple at -0.021 V vs Cp2Fe+/0.