M. Schlaf, A. Lough, R. Morris
Mar 18, 1997
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0
Influential Citations
28
Citations
Journal
Organometallics
Abstract
The complex [RuH(NH2NMe2)3(cod)]PF6, cod = cyclooctadiene, a ruthenium hydride synthon, reacts with 2 equiv of R,R‘-Me-DuPHOS, 1,2-bis((2R,5R)-2,5-dimethylphospholano)benzene, to produce the five-coordinate complex [RuH(R,R‘-Me-DuPHOS)2]PF6. With H2(g) this complex reversibly forms the dihydrogen complex trans-[Ru(η2-H2)H(R,R‘-Me-DuPHOS)2]PF6. The T1(min) at 400 MHz of 9.0 ± 0.5 ms corresponds to an H−H distance of 0.78 A for fast motion of the η2-H2 ligand or 0.99 A for slow motion. The J(H,D) coupling value of the η2-HD isotopomer is 30 Hz. By use of an empirical relationship this corresponds to an H−H distance of 0.92 A. The structure of trans-[Ru(η2-H2)H(R,R‘-Me-DuPHOS)2]PF6 was determined by X-ray. It has approximate C2 symmetry in the solid state and in solution. The η2-H2 ligand is located in a chiral pocket defined by the diphosphine ligands. The five-coordinate complex reacts with N2 (1 atm) at −30 °C to give the thermally unstable complex trans-[Ru(N2)H(R,R‘-Me-DuPHOS)2]PF6, which was characteri...