The complex [RuH(NH 2 NMe 2 ) 3 (cod)]PF 6, cod = cyclooctadiene, a ruthenium hydride synthon, reacts with 2 equiv of R,R‘-Me-DuPHOS, 1,2-bis((2 R,5 R )-2,5-dimethylphospholano)benzene, to produce the five-coordinate complex [RuH(R,R‘-Me-DuPHOS) 2 ]PF 6 . With H 2 (g) this complex reversibly forms the dihydrogen complex trans -[Ru(η 2 -H 2 )H(R,R‘-Me-DuPHOS) 2 ]PF 6 . The T 1 (min) at 400 MHz of 9.0 ± 0.5 ms corresponds to an H−H distance of 0.78 Å for fast motion of the η 2 -H 2 ligand or 0.99 Å for slow motion. The J (H,D) coupling value of the η 2 -HD isotopomer is 30 Hz. By use of an empirical relationship this corresponds to an H−H distance of 0.92 Å. The structure of trans -[Ru(η 2 -H 2 )H(R,R‘-Me-DuPHOS) 2 ]PF 6 was determined by X-ray. It has approximate C 2 symmetry in the solid state and in solution. The η 2 -H 2 ligand is located in a chiral pocket defined by the diphosphine ligands. The five-coordinate complex reacts with N 2 (1 atm) at −30 °C to give the thermally unstable complex trans -[Ru(N 2 )H(R,R‘-Me-DuPHOS) 2 ]PF 6, which was characterized by IR, NMR, elemental analysis, and X-ray diffraction.
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Schlaf et al. (1997) studied this question.
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