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Title: Cluster complexes containing ynamine ligands. 1. Synthesis and structural characterizations of the complexes Os sub 4 (CO) sub 11 (. mu. sub 3 -MeC sub 2 NMe sub 2 )(. mu. -MeC sub 2 NMe sub 2 )(. mu. sub 3 -S), Os sub 4 (CO) sub 11 (. mu. -C(Me)C(NMe sub 2 )C(NMe sub 2 )CMe)(. mu. sub 3 -S), Os sub 4 (CO) sub 11 (. mu. -C(NMe sub 2 )C(Me)C(Me)C(NMe sub 2 ))(. mu. sub 3 -S), Os sub 4 (CO) sub 9 (. mu. -MeC sub 2 NMe sub 2 )(. mu. -C(Me)C(NMe sub 2 )C(Me)C(NMe sub 2 ))-(. mu. sub 3 -S), and Os sub 3 (CO) sub 7 (. mu. sub 3 -MeC sub 2 NMe sub 2 )(. mu. -MeC sub 2 NMe sub 2 )(. mu. sub 3 -S)

Abstract

The reaction of Os{sub 4}(CO){sub 12}({mu}{sub 3}-S) (1) with MeC{sub 2}NMe{sub 2} yielded the complexes Os{sub 3}(CO){sub 9}({mu}{sub 3}-MeC{sub 2}NMe{sub 2})({mu}{sub 3}-S) (2), Os{sub 4}(CO){sub 11}({mu}{sub 3}-MeC{sub 2}NMe{sub 2})({mu}-MeC{sub 2}NMe{sub 2})({mu}{sub 3}-S) (3), Os{sub 4}(CO){sub 11}({mu}-C(Me)C(NMe{sub 2})C(NMe{sub 2})CMe)({mu}{sub 3}-S) (4), Os{sub 4}(CO){sub 11}({mu}-C(NMe{sub 2})C(Me)C(Me)C(NMe{sub 2}))({mu}{sub 3}-S) (5), Os{sub 4}(CO){sub 9}({mu}-MeC{sub 2}NMe{sub 2})({mu}-C(Me)C(NMe{sub 2})C(Me)C(NMe{sub 2}))({mu}{sub 3}-S) (6), and Os{sub 3}(CO){sub 7}({mu}{sub 3}-MeC{sub 2}NMe{sub 2})({mu}-MeC{sub 2}NMe{sub 2})({mu}{sub 3}-S) (7), all in low yields. Compounds 3-7 are new and have been characterized by Ir, {sup 1}H NMR, and single-crystal X-ray diffraction analyses. Compound 3 contains a chain of four osmium atoms with two bridging ynamine ligands and a bridging sulfido ligand. Both ynamine ligands contain strong {pi}-bonding interactions between the NMe{sub 2} groups and the neighboring carbon atom in the alkynyl groups. These interactions alter the metal-carbon bonding, and the ynamine ligands adopt structures that resemble aminocarbene ligands. Similar structures were found for the ynamine ligands in 7. Compounds 4-6 contain spiked triangular clusters of four osmium atoms with a triply bridging sulfido ligand on the triangular grouping. Each of these compounds also contains a metallacyclopentadiene group formed by the coupling of two ynamine ligands. In each compound, the two ynamine ligands havemore » been coupled in a different way. In 4, they were coupled tail to tail. In 5 they were coupled head to head, and in 6 they were coupled head to tail. There is structural evidence for significant, albeit weaker, {pi}-bonding interactions between the amino groups and the adjacent carbon atoms in these complexes. This seems to produce a weakening of the corresponding metal-carbon bonding.« less

Authors:
; ; ; ;  [1]
  1. Univ. of South Carolina, Columbia (USA)
Publication Date:
OSTI Identifier:
6654526
Resource Type:
Journal Article
Journal Name:
Organometallics; (USA)
Additional Journal Information:
Journal Volume: 9:1; Journal ID: ISSN 0276-7333
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; OSMIUM COMPLEXES; SYNTHESIS; CLUSTER MODEL; CRYSTAL STRUCTURE; DATA ANALYSIS; EXPERIMENTAL DATA; LIGANDS; MEASURING INSTRUMENTS; MEASURING METHODS; ORGANOMETALLIC COMPOUNDS; COMPLEXES; DATA; INFORMATION; MATHEMATICAL MODELS; NUCLEAR MODELS; NUMERICAL DATA; ORGANIC COMPOUNDS; TRANSITION ELEMENT COMPLEXES; 400200* - Inorganic, Organic, & Physical Chemistry

Citation Formats

Adams, R D, Chen, Gong, Sun, Sixiu, Tanner, J T, and Wolfe, T A. Cluster complexes containing ynamine ligands. 1. Synthesis and structural characterizations of the complexes Os sub 4 (CO) sub 11 (. mu. sub 3 -MeC sub 2 NMe sub 2 )(. mu. -MeC sub 2 NMe sub 2 )(. mu. sub 3 -S), Os sub 4 (CO) sub 11 (. mu. -C(Me)C(NMe sub 2 )C(NMe sub 2 )CMe)(. mu. sub 3 -S), Os sub 4 (CO) sub 11 (. mu. -C(NMe sub 2 )C(Me)C(Me)C(NMe sub 2 ))(. mu. sub 3 -S), Os sub 4 (CO) sub 9 (. mu. -MeC sub 2 NMe sub 2 )(. mu. -C(Me)C(NMe sub 2 )C(Me)C(NMe sub 2 ))-(. mu. sub 3 -S), and Os sub 3 (CO) sub 7 (. mu. sub 3 -MeC sub 2 NMe sub 2 )(. mu. -MeC sub 2 NMe sub 2 )(. mu. sub 3 -S). United States: N. p., 1990. Web. doi:10.1021/om00115a037.
Adams, R D, Chen, Gong, Sun, Sixiu, Tanner, J T, & Wolfe, T A. Cluster complexes containing ynamine ligands. 1. Synthesis and structural characterizations of the complexes Os sub 4 (CO) sub 11 (. mu. sub 3 -MeC sub 2 NMe sub 2 )(. mu. -MeC sub 2 NMe sub 2 )(. mu. sub 3 -S), Os sub 4 (CO) sub 11 (. mu. -C(Me)C(NMe sub 2 )C(NMe sub 2 )CMe)(. mu. sub 3 -S), Os sub 4 (CO) sub 11 (. mu. -C(NMe sub 2 )C(Me)C(Me)C(NMe sub 2 ))(. mu. sub 3 -S), Os sub 4 (CO) sub 9 (. mu. -MeC sub 2 NMe sub 2 )(. mu. -C(Me)C(NMe sub 2 )C(Me)C(NMe sub 2 ))-(. mu. sub 3 -S), and Os sub 3 (CO) sub 7 (. mu. sub 3 -MeC sub 2 NMe sub 2 )(. mu. -MeC sub 2 NMe sub 2 )(. mu. sub 3 -S). United States. doi:10.1021/om00115a037.
Adams, R D, Chen, Gong, Sun, Sixiu, Tanner, J T, and Wolfe, T A. Mon . "Cluster complexes containing ynamine ligands. 1. Synthesis and structural characterizations of the complexes Os sub 4 (CO) sub 11 (. mu. sub 3 -MeC sub 2 NMe sub 2 )(. mu. -MeC sub 2 NMe sub 2 )(. mu. sub 3 -S), Os sub 4 (CO) sub 11 (. mu. -C(Me)C(NMe sub 2 )C(NMe sub 2 )CMe)(. mu. sub 3 -S), Os sub 4 (CO) sub 11 (. mu. -C(NMe sub 2 )C(Me)C(Me)C(NMe sub 2 ))(. mu. sub 3 -S), Os sub 4 (CO) sub 9 (. mu. -MeC sub 2 NMe sub 2 )(. mu. -C(Me)C(NMe sub 2 )C(Me)C(NMe sub 2 ))-(. mu. sub 3 -S), and Os sub 3 (CO) sub 7 (. mu. sub 3 -MeC sub 2 NMe sub 2 )(. mu. -MeC sub 2 NMe sub 2 )(. mu. sub 3 -S)". United States. doi:10.1021/om00115a037.
@article{osti_6654526,
title = {Cluster complexes containing ynamine ligands. 1. Synthesis and structural characterizations of the complexes Os sub 4 (CO) sub 11 (. mu. sub 3 -MeC sub 2 NMe sub 2 )(. mu. -MeC sub 2 NMe sub 2 )(. mu. sub 3 -S), Os sub 4 (CO) sub 11 (. mu. -C(Me)C(NMe sub 2 )C(NMe sub 2 )CMe)(. mu. sub 3 -S), Os sub 4 (CO) sub 11 (. mu. -C(NMe sub 2 )C(Me)C(Me)C(NMe sub 2 ))(. mu. sub 3 -S), Os sub 4 (CO) sub 9 (. mu. -MeC sub 2 NMe sub 2 )(. mu. -C(Me)C(NMe sub 2 )C(Me)C(NMe sub 2 ))-(. mu. sub 3 -S), and Os sub 3 (CO) sub 7 (. mu. sub 3 -MeC sub 2 NMe sub 2 )(. mu. -MeC sub 2 NMe sub 2 )(. mu. sub 3 -S)},
author = {Adams, R D and Chen, Gong and Sun, Sixiu and Tanner, J T and Wolfe, T A},
abstractNote = {The reaction of Os{sub 4}(CO){sub 12}({mu}{sub 3}-S) (1) with MeC{sub 2}NMe{sub 2} yielded the complexes Os{sub 3}(CO){sub 9}({mu}{sub 3}-MeC{sub 2}NMe{sub 2})({mu}{sub 3}-S) (2), Os{sub 4}(CO){sub 11}({mu}{sub 3}-MeC{sub 2}NMe{sub 2})({mu}-MeC{sub 2}NMe{sub 2})({mu}{sub 3}-S) (3), Os{sub 4}(CO){sub 11}({mu}-C(Me)C(NMe{sub 2})C(NMe{sub 2})CMe)({mu}{sub 3}-S) (4), Os{sub 4}(CO){sub 11}({mu}-C(NMe{sub 2})C(Me)C(Me)C(NMe{sub 2}))({mu}{sub 3}-S) (5), Os{sub 4}(CO){sub 9}({mu}-MeC{sub 2}NMe{sub 2})({mu}-C(Me)C(NMe{sub 2})C(Me)C(NMe{sub 2}))({mu}{sub 3}-S) (6), and Os{sub 3}(CO){sub 7}({mu}{sub 3}-MeC{sub 2}NMe{sub 2})({mu}-MeC{sub 2}NMe{sub 2})({mu}{sub 3}-S) (7), all in low yields. Compounds 3-7 are new and have been characterized by Ir, {sup 1}H NMR, and single-crystal X-ray diffraction analyses. Compound 3 contains a chain of four osmium atoms with two bridging ynamine ligands and a bridging sulfido ligand. Both ynamine ligands contain strong {pi}-bonding interactions between the NMe{sub 2} groups and the neighboring carbon atom in the alkynyl groups. These interactions alter the metal-carbon bonding, and the ynamine ligands adopt structures that resemble aminocarbene ligands. Similar structures were found for the ynamine ligands in 7. Compounds 4-6 contain spiked triangular clusters of four osmium atoms with a triply bridging sulfido ligand on the triangular grouping. Each of these compounds also contains a metallacyclopentadiene group formed by the coupling of two ynamine ligands. In each compound, the two ynamine ligands have been coupled in a different way. In 4, they were coupled tail to tail. In 5 they were coupled head to head, and in 6 they were coupled head to tail. There is structural evidence for significant, albeit weaker, {pi}-bonding interactions between the amino groups and the adjacent carbon atoms in these complexes. This seems to produce a weakening of the corresponding metal-carbon bonding.},
doi = {10.1021/om00115a037},
journal = {Organometallics; (USA)},
issn = {0276-7333},
number = ,
volume = 9:1,
place = {United States},
year = {1990},
month = {1}
}