Theoretical predictions and single-crystal neutron diffraction and inelastic neutron scattering studies on the reaction of dihydrogen with the dinuclear dinitrogen complex of zirconium [P2N2]Zr(mu-eta(2)-N-2)Zr[P2N2], P2N2=PhP(CH2SiMe2NSiMe2CH2)(2)PPh
H. Basch et al., Theoretical predictions and single-crystal neutron diffraction and inelastic neutron scattering studies on the reaction of dihydrogen with the dinuclear dinitrogen complex of zirconium [P2N2]Zr(mu-eta(2)-N-2)Zr[P2N2], P2N2=PhP(CH2SiMe2NSiMe2CH2)(2)PPh, J AM CHEM S, 121(3), 1999, pp. 523-528
A single-crystal neutron diffraction analysis along with density functional
calculations and incoherent inelastic neutron scattering studies has concl
usively shown that the dihydrogen adduct of [P2N2]Zr(mu-eta(2)-N-2)Zr[P2N2]
(1) (where P2N2 = PhP(CH2SiMe2NSiMe2CH2)(2)PPh) is [P2N2]Zr(mu-eta(2)-N2H)
(mu-H)Zr[P2N2] (2), the complex with a bridging hydride and a N-N-H moiety,
and not the dihydrogen complex [P2N2]Zr(mu-eta(2)-N-2)(mu-eta(2)-H-2)Zr[P2
N2] (3), as was proposed on the basis of X-ray crystallographic data. In ad
dition, DFT calculations show that the reaction of 1 with both H-2 and SiH4
is exothermic while an endothermic reaction is found for the reaction of 1
with CH4.