PREPARATION AND PROPERTIES OF DIAZENIDO, HYDRAZIDO(2-), AND HYDRIDO-HYDRAZIDO(2-) COMPLEXES OF TUNGSTEN. X-RAY PHOTOELECTRON SPECTROSCOPY OF DINITROGEN AND HYDRAZIDO(2-) COMPLEXES OF MOLYBDENUM AND TUNGSTEN
Titel:
PREPARATION AND PROPERTIES OF DIAZENIDO, HYDRAZIDO(2-), AND HYDRIDO-HYDRAZIDO(2-) COMPLEXES OF TUNGSTEN. X-RAY PHOTOELECTRON SPECTROSCOPY OF DINITROGEN AND HYDRAZIDO(2-) COMPLEXES OF MOLYBDENUM AND TUNGSTEN
Auteur:
George, T. Adrian Kwarcinski, Michael E.
Verschenen in:
Journal of coordination chemistry
Paginering:
Jaargang 35 (1995) nr. 3-4 pagina's 349-357
Jaar:
1995-07-01
Inhoud:
Reactions of HBr with trans-[W(N2)2(dppe)PPh2Me)2] (1) (dppe = Ph2CH2CH2PPh2) result in protonation of coordinated N2 but no formation of ammonia or hydrazine. The tungsten-containing product depends upon the reaction conditions: (i) in MeOH, the product formed is [WBr(NNH2) (dppe)(PPh2Me)2]HBr2 (2) which converts to the hydride, [WBr2(H)(NNH2(dppe)(PPh2Me)](Br(3), with loss of phosphine in THF or CH2Cl2, (ii) in THF or CH2Cl2, the hydride (3) is formed directly. Reaction of 2 with Na2CO3 in MeOH results in the loss of HBr and the formation of the diazenido complex [WBr(NNH)(dppe)(PPh2Me)2] which reacts further with Na2CO3 in benzene under N2 to lose HBr and form a mixture of 1 and trans-[W(N2)(dppe)2]. The reaction of 1 with aqueous HF forms [WF(NNH2)(dppe)(PPh2Me)2]BF4. The X-ray photoelectron spectra of trans-[M(N2)2 (dppe)2], [MBr(NNH2)(dppe)2Br (M = Mo, W), [WCl(NNH2)(dppe)2]Cl, [WCl(N)(dppe)2]Cl and [WCl(NH) (dppe)2] are reported. In all of these complexes, nitrogen is in a highly reduced form.
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