| Abstract | The hitherto unknown series of complexes fac-[Re(CO)3Br{R2P(S)P(S)R2}] 1a-5a (1a, R=Me; 2a, R=Et; 3a, R=nPr; 4a, R=nBu; 5a, R=Ph) and [Re2(CO)8Br2{cis-[mu]-R2P(S)P(S)R2}] 1b-5b [1b, R=Me; 2b, R=Et; 3b, R=nPr; 4b, R=nBu; 5b, R=Ph] have been prepared by the photochemical reaction of Re(CO)5Br with R2P(S)P(S)R2. The complexes have been characterized by elemental analysis, mass spectroscopy (EI), FT-IR and 31P{1H} NMR spectrometry. The spectroscopic studies suggest cis-chelate bidentate coordination of the ligand in fac-[Re(CO)3Br{R2P(S)P(S)R2}] and cis-bridging bidentate coordination of the ligand between two metals in [Re2(CO)8Br2{cis-[mu]-R2P(S)P(S)R2}] (R=Me, Et, nPr, nBu, Ph). An X-ray diffraction study of [ReBr(CO)3(Et2P(S)P(S)Et2)] confirms that the rhenium adopts a distorted octahedral geometry with local Cs symmetry. |
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