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]

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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), Vol. 112:11; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

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