184014-37-7Relevant academic research and scientific papers
Characterization of Five-Coordinate Ruthenium(II) Phosphine Complexes by X-ray Diffraction and Solid-State 31P CP/MAS NMR Studies and Their Reactivity with Sulfoxides and Thioethers
MacFarlane, Kenneth S.,Joshi, Ajey M.,Rettig, Steven J.,James, Brian R.
, p. 7304 - 7310 (1996)
31P CP/MAS NMR spectroscopy is examined as a method of characterization for ruthenium(II) phosphine complexes in the solid state, and the results are compared with X-ray crystallographic data determined for RuCl2(dppb)(PPh3) (dppb = Ph2P(CH2)4PPh2), RuBr2(PPh3)3, and the previously determined RuCl2(PPh3)3. Crystals of RuBr2(PPh3)3 (C54H45Br2P3Ru) are monoclinic, space group P21/a, with a = 12.482(4) ?, b = 20.206(6) ?, c = 17.956(3) ?, β = 90.40(2)°, and Z = 4, and those of RuCl2(dppb)(PPh3) (C46H43Cl2P3Ru) are also monoclinic, space group P21/n, with a = 10.885(2) ?, b = 20.477(1) ?, c = 18.292(2) ?, β = 99.979(9)°, and Z = 4. The structure of RuBr2(PPh3)3 was solved by direct methods, and that of RuCl2(dppb)(PPh3) was solved by the Patterson method. The structures were refined by full-matrix least-squares procedures to R = 0.048 and 0.031 (Rw = 0.046 and 0.032) for 5069 and 5925 reflections with I ≥ 3σ(I), respectively. Synthetic routes to RuBr2(dppb)(PPh3) and [RuBr(dppb)]2(μ2-dppb) are reported. The reactivity of RuCl2(dppb)(PPh3) with the neutral two-electron donor ligands (L) dimethyl sulfoxide, tetramethylene sulfoxide, tetrahydrothiophene, and dimethyl sulfide to give [(L)-(dppb)Ru(μ-Cl)3RuCl(dppb)] is discussed.
