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Title: A study of high oxidation state complexes of the type (W(. eta. sup 5 -C sub 5 Me sub 5 )Me sub 2 X) sub 2 (. mu. -N sub 2 ), including X-ray structures of (W(. eta. sup 5 -C sub 5 Me sub 5 )Me sub 2 (OC sub 6 F sub 5 ))(. mu. -N sub 2 ) and (W(. eta. sup 5 -C sub 5 Me sub 5 )Me sub 2 (S-2,4,6-C sub 6 H sub 2 Me sub 3 )) sub 2 (. mu. -N sub 2 )

Abstract

A high yield route (80-90%) to the bridging dinitrogen complex (WCp{sup *}Me{sub 3}){sub 2}({mu}-N{sub 2}) (1) consists of the reduction of WCp{sup *}Me{sub 3}(OTf) by sodium amalgam in the presence of dinitrogen. 1 reacts with HOTf (2 or excess (6) equiv) to give (WCp{sup *}Me{sub 2}(OTf)){sub 2}({mu}-N{sub 2}) or (WCp{sup *}Me(OTf){sub 2}){sub 2}({mu}-N{sub 2}), respectively, with C{sub 6}F{sub 5}COOH, C{sub 6}F{sub 5}OH, or C{sub 6}F{sub 5}SH to give complexes of the form (WCp{sup *}Me{sub 2}(X)){sub 2}({mu}-N{sub 2}) (X = OC{sub 6}F{sub 5}, etc.), and with tetrabromocatechol to give (WCp{sup *}Me(O{sub 2}C{sub 6}Br{sub 4})){sub 2}({mu}-N{sub 2}). (WCp{sup *}Me{sub 2}(OTf)){sub 2}({mu}-N{sub 2}) reacts with NaSR (R = 2,4,6-C{sub 6}H{sub 2}Me{sub 3} or 2,4,6-C{sub 6}H{sub 2}-i-Pr{sub 3}) to give complexes of the form (WCp{sup *}Me{sub 2}(SR)){sub 2}({mu}-N{sub 2}), and (WCp{sup *}Me(OTf){sub 2}){sub 2}({mu}-N{sub 2}) and (WCp{sup *}Me{sub 2}(S-2,4,6-C{sub 6}H{sub 2}Me{sub 3})){sub 2}({mu}-N{sub 2}) show that the complexes have structures that are similar to that of 1, except the N-N bond lengths are shorter.

Authors:
; ; ; ;  [1]
  1. Massachusetts Institute of Technology, Cambridge (USA)
Publication Date:
OSTI Identifier:
6611922
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society; (USA)
Additional Journal Information:
Journal Volume: 112:11; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; TUNGSTEN COMPLEXES; CRYSTAL STRUCTURE; SYNTHESIS; DATA ANALYSIS; EXPERIMENTAL DATA; MEASURING INSTRUMENTS; MEASURING METHODS; ORGANOMETALLIC COMPOUNDS; X-RAY DIFFRACTION; COHERENT SCATTERING; COMPLEXES; DATA; DIFFRACTION; INFORMATION; NUMERICAL DATA; ORGANIC COMPOUNDS; SCATTERING; TRANSITION ELEMENT COMPLEXES; 550200* - Biochemistry

Citation Formats

O'Regan, M B, Liu, A H, Finch, W C, Schrock, R R, and Davis, W M. A study of high oxidation state complexes of the type (W(. eta. sup 5 -C sub 5 Me sub 5 )Me sub 2 X) sub 2 (. mu. -N sub 2 ), including X-ray structures of (W(. eta. sup 5 -C sub 5 Me sub 5 )Me sub 2 (OC sub 6 F sub 5 ))(. mu. -N sub 2 ) and (W(. eta. sup 5 -C sub 5 Me sub 5 )Me sub 2 (S-2,4,6-C sub 6 H sub 2 Me sub 3 )) sub 2 (. mu. -N sub 2 ). United States: N. p., 1990. Web. doi:10.1021/ja00167a033.
O'Regan, M B, Liu, A H, Finch, W C, Schrock, R R, & Davis, W M. A study of high oxidation state complexes of the type (W(. eta. sup 5 -C sub 5 Me sub 5 )Me sub 2 X) sub 2 (. mu. -N sub 2 ), including X-ray structures of (W(. eta. sup 5 -C sub 5 Me sub 5 )Me sub 2 (OC sub 6 F sub 5 ))(. mu. -N sub 2 ) and (W(. eta. sup 5 -C sub 5 Me sub 5 )Me sub 2 (S-2,4,6-C sub 6 H sub 2 Me sub 3 )) sub 2 (. mu. -N sub 2 ). United States. https://doi.org/10.1021/ja00167a033
O'Regan, M B, Liu, A H, Finch, W C, Schrock, R R, and Davis, W M. 1990. "A study of high oxidation state complexes of the type (W(. eta. sup 5 -C sub 5 Me sub 5 )Me sub 2 X) sub 2 (. mu. -N sub 2 ), including X-ray structures of (W(. eta. sup 5 -C sub 5 Me sub 5 )Me sub 2 (OC sub 6 F sub 5 ))(. mu. -N sub 2 ) and (W(. eta. sup 5 -C sub 5 Me sub 5 )Me sub 2 (S-2,4,6-C sub 6 H sub 2 Me sub 3 )) sub 2 (. mu. -N sub 2 )". United States. https://doi.org/10.1021/ja00167a033.
@article{osti_6611922,
title = {A study of high oxidation state complexes of the type (W(. eta. sup 5 -C sub 5 Me sub 5 )Me sub 2 X) sub 2 (. mu. -N sub 2 ), including X-ray structures of (W(. eta. sup 5 -C sub 5 Me sub 5 )Me sub 2 (OC sub 6 F sub 5 ))(. mu. -N sub 2 ) and (W(. eta. sup 5 -C sub 5 Me sub 5 )Me sub 2 (S-2,4,6-C sub 6 H sub 2 Me sub 3 )) sub 2 (. mu. -N sub 2 )},
author = {O'Regan, M B and Liu, A H and Finch, W C and Schrock, R R and Davis, W M},
abstractNote = {A high yield route (80-90%) to the bridging dinitrogen complex (WCp{sup *}Me{sub 3}){sub 2}({mu}-N{sub 2}) (1) consists of the reduction of WCp{sup *}Me{sub 3}(OTf) by sodium amalgam in the presence of dinitrogen. 1 reacts with HOTf (2 or excess (6) equiv) to give (WCp{sup *}Me{sub 2}(OTf)){sub 2}({mu}-N{sub 2}) or (WCp{sup *}Me(OTf){sub 2}){sub 2}({mu}-N{sub 2}), respectively, with C{sub 6}F{sub 5}COOH, C{sub 6}F{sub 5}OH, or C{sub 6}F{sub 5}SH to give complexes of the form (WCp{sup *}Me{sub 2}(X)){sub 2}({mu}-N{sub 2}) (X = OC{sub 6}F{sub 5}, etc.), and with tetrabromocatechol to give (WCp{sup *}Me(O{sub 2}C{sub 6}Br{sub 4})){sub 2}({mu}-N{sub 2}). (WCp{sup *}Me{sub 2}(OTf)){sub 2}({mu}-N{sub 2}) reacts with NaSR (R = 2,4,6-C{sub 6}H{sub 2}Me{sub 3} or 2,4,6-C{sub 6}H{sub 2}-i-Pr{sub 3}) to give complexes of the form (WCp{sup *}Me{sub 2}(SR)){sub 2}({mu}-N{sub 2}), and (WCp{sup *}Me(OTf){sub 2}){sub 2}({mu}-N{sub 2}) and (WCp{sup *}Me{sub 2}(S-2,4,6-C{sub 6}H{sub 2}Me{sub 3})){sub 2}({mu}-N{sub 2}) show that the complexes have structures that are similar to that of 1, except the N-N bond lengths are shorter.},
doi = {10.1021/ja00167a033},
url = {https://www.osti.gov/biblio/6611922}, journal = {Journal of the American Chemical Society; (USA)},
issn = {0002-7863},
number = ,
volume = 112:11,
place = {United States},
year = {Wed May 23 00:00:00 EDT 1990},
month = {Wed May 23 00:00:00 EDT 1990}
}