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 )

O'Regan, M B; Liu, A H; Finch, W C; Schrock, R R; Davis, W M

doi:10.1021/ja00167a033

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 )

Journal Article · Wed May 23 00:00:00 EDT 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00167a033· OSTI ID:6611922

O'Regan, M B; Liu, A H; Finch, W C; Schrock, R R; Davis, W M ^[1]

Massachusetts Institute of Technology, Cambridge (USA)

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.

OSTI ID:: 6611922

Journal Information:: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:11; ISSN 0002-7863; ISSN JACSA

Country of Publication:: United States

Language:: English

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Related Subjects

550200* -- Biochemistry
59 BASIC BIOLOGICAL SCIENCES
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
DIFFRACTION
EXPERIMENTAL DATA
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
SCATTERING
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES
X-RAY DIFFRACTION

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