Synthesis, Characterization, and X‐ray Structures of Ru3(CO)9(dotpm)(L) Complexes [L = PPh3, P(C6H4Cl‐p)3, and PPh2(C6H4Br‐p)]

The reaction of Ru3(CO)10(dotpm) (1) [dotpm = (bis(di-ortho-tolylphosphanyl)methane)] and one equivalent of L [L = PPh3, P(C6H4Cl-p)3 and PPh2(C6H4Br-p)] in refluxing n-hexane afforded a series of derivatives [Ru3(CO)9(dotpm)L] (2–4), respectively, in ca. 67–70 % yield. Complexes 2–4 were characterized by elemental analysis (CHN), IR, 1H NMR, 13C{1H} NMR and 31P{1H} NMR spectroscopy. The molecular structures of 2, 3, and 4 were established by single-crystal X-ray diffraction. The bidentate dotpm and monodentate phosphine ligands occupy equatorial positions with respect to the Ru triangle. The effect of substitution resulted in significant differences in the Ru–Ru and Ru–P bond lengths.

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