Synthesis, spectroscopic characterization and crystal and molecular structure of HRu 3(OCN(CH 3) 2)(CO) 10

Abstract

Dimethylamine reacts with Ru 3(CO) 12 to produce the η 2-hydrido-η-formamido cluster complex HRu(OCN(CH 3) 2)(CO) 10 (I). This formulation is consistent with spectroscopic features such as the absence of v(NH) in the infrared, the presence in the Raman of v(RuHRu) at 1400 cm −1 ( v(RuDRu) at 990 cm −1) and indication in the 1H NMR of diastereotopic methyl groups bonded to the nitrogen atom. Since these data could not lead to an unequivocal structure assignment a single crystal X-ray study at 115 K was undertaken. The complex crystallizes in the triclinic space group, P 1 with cell dimensions; a 7.299(33) », b 9.5037(40) », c 13.7454(57) », α 91.876(34)°, β 96.387(34)°, γ 95.341(34)° and Z = 2. The structure was solved by a combination of Patterson and Fourier techniques and refined by full matrix least squares to a final R = 0.054 and R ω = 0.074 for 3074 unique reflections. The three ruthenium atoms define a triangle of unequal sides with both the hydride and formamido groups bridging the longest edge; the formamido group is coordinated through the carbon and oxygen atoms. The edge of the ruthenium triangle bridged both by the hydrogen atom and the formamido group is 2.8755(15) »; the other two edges of the ruthenium triangle are observed to be 2.8319(15) and 2.8577(14) », respectively. In the formamido group the distance CO 1.287(9) » and CN 1.340(10) » reflect partial double bond charater in each bond consistent with observation of two chemically distinct methyl groups on the dinitrogen atom. The hydrogen atom bridging one edge of the ruthenium triangle is asymmetrically positioned at 1.73(9) » from the ruthenium atom bonded to the oxygen atom and 1.91(9) » from the ruthenium atom bonded to the carbon atom of the carboxamido group.