Diamagnetic (Pentamethylcyclopentadienyl)tungsten complexes containing unsubstituted, monomethyl, or 1,1-dimethyl hyrazine or hydrazido ligands
- Massachusetts Inst. of Technology, Cambridge, MA (United States)
Hydrazine adducts are formed upon adding hydrazine, methylhydrazine, or 1,1-dimethylhydrazine to [Cp*WMe{sub 4}]PF{sub 6}. They are readily deprotonated to yield hydrazido(1-) complexes of the type Cp*WMe{sub 4}[{eta}{sup 2}-hydrazido(1-)], or they decompose by loss of methane to yield complexes of the type (Cp*WMe{sub 3}[{eta}{sup 2}-hydrazido (1-)]){sup +}. [Cp*WMe{sub 3} ({eta}{sup 2}-NHNH{sub 2})] Cl decomposes much more readily than the triflate salt by losing methane to give trans-Cp*WMe{sub 2}Cl({eta}{sup 1}-NNH{sub 2}). Methylation of Cp*WMe{sub 3}({eta}{sup 1}-NNMe{sub 2}) yields [Cp*WMe{sub 3}(NNMe{sub 3})]{sup +}; [Cp*WMe{sub 3}(NNMe{sub 3})]{sup +} also is obtained upon methylating Cp*WMe{sub 3}({eta}{sup 1}-NNH{sub 2}) in the presence of a base. These findings and other reactions are discussed in relation to the proposal that both nitrogen atoms of an N{sub 2}H{sub x} intermediate must bind to the metal in preparation for formation of a d{sup 2} {eta}{sup 2}-N{sub 2}H{sub 4} complex in which the N-N bond is cleaved to yield 1 equiv of ammonia. It was found that the n{sup 2} may be required for efficient cleavage of the N-N bond in systems of this type. 54 refs., 6 figs., 5 tabs.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 457064
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 21 Vol. 114; ISSN JACSAT; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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