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Title: Diamagnetic (Pentamethylcyclopentadienyl)tungsten complexes containing unsubstituted, monomethyl, or 1,1-dimethyl hyrazine or hydrazido ligands

Abstract

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.

Authors:
; ;  [1]
  1. Massachusetts Inst. of Technology, Cambridge, MA (United States)
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
457064
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 114; Journal Issue: 21; Other Information: PBD: 7 Oct 1992
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; TUNGSTEN COMPLEXES; ELECTRONIC STRUCTURE; CHEMICAL REACTION KINETICS; ADDUCTS; HYDRAZINE; METHYLATION; DIAMAGNETISM

Citation Formats

Glassman, T E, Vale, M G, and Schrock, R R. Diamagnetic (Pentamethylcyclopentadienyl)tungsten complexes containing unsubstituted, monomethyl, or 1,1-dimethyl hyrazine or hydrazido ligands. United States: N. p., 1992. Web. doi:10.1021/ja00047a019.
Glassman, T E, Vale, M G, & Schrock, R R. Diamagnetic (Pentamethylcyclopentadienyl)tungsten complexes containing unsubstituted, monomethyl, or 1,1-dimethyl hyrazine or hydrazido ligands. United States. https://doi.org/10.1021/ja00047a019
Glassman, T E, Vale, M G, and Schrock, R R. Wed . "Diamagnetic (Pentamethylcyclopentadienyl)tungsten complexes containing unsubstituted, monomethyl, or 1,1-dimethyl hyrazine or hydrazido ligands". United States. https://doi.org/10.1021/ja00047a019.
@article{osti_457064,
title = {Diamagnetic (Pentamethylcyclopentadienyl)tungsten complexes containing unsubstituted, monomethyl, or 1,1-dimethyl hyrazine or hydrazido ligands},
author = {Glassman, T E and Vale, M G and Schrock, R R},
abstractNote = {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.},
doi = {10.1021/ja00047a019},
url = {https://www.osti.gov/biblio/457064}, journal = {Journal of the American Chemical Society},
number = 21,
volume = 114,
place = {United States},
year = {1992},
month = {10}
}