Theoretical predictions and single-crystal neutron diffraction and inelastic neutron scattering studies on the reaction of dihydrogen with the dinuclear dinitrogen complex of zirconium [P{sub 2}N{sub 2}]Zr({mu}-{eta}{sup 2}-N{sub 2})Zr[P{sub 2}N{sub 2}], P{sub 2}N{sub 2} = PhP(CH{sub 2}SiMe{sub 2}NSiMe{sub 2}CH{sub 2}){sub 2}PPh
- and others
A single-crystal neutron diffraction analysis along with density functional calculations and incoherent inelastic neutron scattering studies has conclusively shown that the dihydrogen adduct of [P{sub 2}N{sub 2}]Zr({mu}-{eta}{sup 2}-N{sub 2})-Zr[P{sub 2}N{sub 2}] (1) (where P{sub 2}N{sub 2} = PhP(CH{sub 2}SiMe{sub 2}NSiMe{sub 2}CH{sub 2}){sub 2}PPH) is [P{sub 2}N{sub 2}]Zr({mu}-{eta}{sup 2}-N{sub 2}H)({mu}-H)Zr[P{sub 2}N{sub 2}] (2), the complex with a bridging hydride and a N-N-H moiety, and not the dihydrogen complex [P{sub 2}N{sub 2}]Zr({mu}-{eta}{sup 2}-N{sub 2})({mu}-{eta}{sup 2}-H{sub 2})Zr[P{sub 2}N{sub 2}] (3), as was proposed on the basis of X-ray crystallographic data. In addition, DFT calculations show that the reaction of 1 with both H{sub 2} and SiH{sub 4} is exothermic while an endothermic reaction is found for the reaction of 1 with CH{sub 4}.
- Research Organization:
- Emory Univ., Atlanta, GA (US)
- Sponsoring Organization:
- Alexander von Humboldt Foundation; USDOE
- DOE Contract Number:
- AC02-98CH10886
- OSTI ID:
- 20014087
- Journal Information:
- Journal of the American Chemical Society, Vol. 121, Issue 3; Other Information: PBD: 27 Jan 1999; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
Similar Records
Classical, nonclassical, and mixed-metal osmium(II) polyhydrides stabilized by the tetraphosphine P(CH[sub 2]CH[sub 2]PPh[sub 2])[sub 3]. H/D isotope exchange reactions promoted by a strongly bound dihydrogen ligand
Classical and nonclassical polyhydride ruthenium(II) complexes stabilized by the tetraphosphine P(CH sub 2 CH sub 2 PPh sub 2 ) sub 3