skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Hydrazido(1-) and 2,2-dimethylhydrazido(1-) derivatives of permethylscandocene. Preparation and structural characterization of their products from reactions with acetonitrile: (. eta. sup 5 -C sub 5 Me sub 5 ) sub 2 ScN(H)C(CH sub 3 )NNH sub 2 and (. eta. sup 5 -C sub 5 Me sub 5 ) sub 2 ScN(H)C(CH sub 3 )NNMe sub 2

Abstract

A rare example of an unsubstituted hydrazido(1-) complex, Cp{sup *}{sub 2}ScN(H)NH{sub 2} (Cp{sup *} = ({eta}{sup 5}-C{sub 5}Me{sub 5})), prepared by reaction of 1 equiv of anhydrous hydrazine with Cp{sup *}{sub 2}ScCH{sub 3}, reacts with acetonitrile to form Cp{sup *}{sub 2}ScN(H)C(CH{sub 3})NNH{sub 2}. The crystal structure of the complex is reported and reveals a five-membered, nearly planar (ScN(H)C(CH{sub 3})NNH{sub 2}) ring. The results of a labeling study using {sup 15}N{triple bond}CCH{sub 3} are consistent with a mechanism involving insertion of acetonitrile into the Sc-N bond of Cp{sup *}{sub 2}ScNHNH{sub 2}, followed by tautomerization to form Cp{sup *}{sub 2}ScN(H)C(CH{sub 3})NNH{sub 2}. The closely related compounds Cp{sup *}{sub 2}ScN(H)NMe{sub 2} and Cp{sup *}{sub 2}ScN(H)C(CH{sub 3})NNMe{sub 2} also have been prepared by using an analogous reaction pathway, and the structure of the latter has been determined as well, revealing a four-membered, nearly planar (ScN(H)C(CH{sub 3})N(NMe{sub 2})) ring. 18 refs., 3 figs., 5 tabs.

Authors:
; ; ;  [1]
  1. California Institute of Technology, Pasadena (USA)
Publication Date:
OSTI Identifier:
5972958
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry; (USA)
Additional Journal Information:
Journal Volume: 29:22; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CYCLOALKANES; CHEMICAL PREPARATION; NITROGEN COMPOUNDS; ORGANOMETALLIC COMPOUNDS; SCANDIUM COMPLEXES; CRYSTAL STRUCTURE; EXPERIMENTAL DATA; LABELLED COMPOUNDS; NITROGEN 15; ALKANES; COMPLEXES; DATA; HYDROCARBONS; INFORMATION; ISOTOPES; LIGHT NUCLEI; NITROGEN ISOTOPES; NUCLEI; NUMERICAL DATA; ODD-EVEN NUCLEI; ORGANIC COMPOUNDS; STABLE ISOTOPES; SYNTHESIS; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties

Citation Formats

Shapiro, P J, Henling, L M, Marsh, R E, and Bercaw, J E. Hydrazido(1-) and 2,2-dimethylhydrazido(1-) derivatives of permethylscandocene. Preparation and structural characterization of their products from reactions with acetonitrile: (. eta. sup 5 -C sub 5 Me sub 5 ) sub 2 ScN(H)C(CH sub 3 )NNH sub 2 and (. eta. sup 5 -C sub 5 Me sub 5 ) sub 2 ScN(H)C(CH sub 3 )NNMe sub 2. United States: N. p., 1990. Web. doi:10.1021/ic00347a045.
Shapiro, P J, Henling, L M, Marsh, R E, & Bercaw, J E. Hydrazido(1-) and 2,2-dimethylhydrazido(1-) derivatives of permethylscandocene. Preparation and structural characterization of their products from reactions with acetonitrile: (. eta. sup 5 -C sub 5 Me sub 5 ) sub 2 ScN(H)C(CH sub 3 )NNH sub 2 and (. eta. sup 5 -C sub 5 Me sub 5 ) sub 2 ScN(H)C(CH sub 3 )NNMe sub 2. United States. https://doi.org/10.1021/ic00347a045
Shapiro, P J, Henling, L M, Marsh, R E, and Bercaw, J E. Wed . "Hydrazido(1-) and 2,2-dimethylhydrazido(1-) derivatives of permethylscandocene. Preparation and structural characterization of their products from reactions with acetonitrile: (. eta. sup 5 -C sub 5 Me sub 5 ) sub 2 ScN(H)C(CH sub 3 )NNH sub 2 and (. eta. sup 5 -C sub 5 Me sub 5 ) sub 2 ScN(H)C(CH sub 3 )NNMe sub 2". United States. https://doi.org/10.1021/ic00347a045.
@article{osti_5972958,
title = {Hydrazido(1-) and 2,2-dimethylhydrazido(1-) derivatives of permethylscandocene. Preparation and structural characterization of their products from reactions with acetonitrile: (. eta. sup 5 -C sub 5 Me sub 5 ) sub 2 ScN(H)C(CH sub 3 )NNH sub 2 and (. eta. sup 5 -C sub 5 Me sub 5 ) sub 2 ScN(H)C(CH sub 3 )NNMe sub 2},
author = {Shapiro, P J and Henling, L M and Marsh, R E and Bercaw, J E},
abstractNote = {A rare example of an unsubstituted hydrazido(1-) complex, Cp{sup *}{sub 2}ScN(H)NH{sub 2} (Cp{sup *} = ({eta}{sup 5}-C{sub 5}Me{sub 5})), prepared by reaction of 1 equiv of anhydrous hydrazine with Cp{sup *}{sub 2}ScCH{sub 3}, reacts with acetonitrile to form Cp{sup *}{sub 2}ScN(H)C(CH{sub 3})NNH{sub 2}. The crystal structure of the complex is reported and reveals a five-membered, nearly planar (ScN(H)C(CH{sub 3})NNH{sub 2}) ring. The results of a labeling study using {sup 15}N{triple bond}CCH{sub 3} are consistent with a mechanism involving insertion of acetonitrile into the Sc-N bond of Cp{sup *}{sub 2}ScNHNH{sub 2}, followed by tautomerization to form Cp{sup *}{sub 2}ScN(H)C(CH{sub 3})NNH{sub 2}. The closely related compounds Cp{sup *}{sub 2}ScN(H)NMe{sub 2} and Cp{sup *}{sub 2}ScN(H)C(CH{sub 3})NNMe{sub 2} also have been prepared by using an analogous reaction pathway, and the structure of the latter has been determined as well, revealing a four-membered, nearly planar (ScN(H)C(CH{sub 3})N(NMe{sub 2})) ring. 18 refs., 3 figs., 5 tabs.},
doi = {10.1021/ic00347a045},
url = {https://www.osti.gov/biblio/5972958}, journal = {Inorganic Chemistry; (USA)},
issn = {0020-1669},
number = ,
volume = 29:22,
place = {United States},
year = {1990},
month = {10}
}