Synthesis and structure of (eta-C/sub 5/H/sub 5/)W(PPh/sub 3/)(CO)(CSPh): transformation of a thiocarbonyl ligand into a carbyne ligand

Journal Article · Tue Dec 04 23:00:00 EST 1979 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00519a028· OSTI ID:5773546

Greaves, W W; Angelici, R J; Helland, B J; Klima, R; Jacobson, R A

The arylation reaction (eta-C/sub 5/H/sub 5/)W(PPh/sub 3/)(CO)(CS)I + LiPh ..-->.. (eta-C/sub 5/H/sub 5/)W(PPh/sub 3/)(CO)(CSPh) + LiI (5) reduces the multiple bonding in the terminal CS ligand of (eta-C/sub 5/H/sub 5/)W(PPh/sub 3/)(CO)(CS)I to a C-S single bond in the carbyne product. The previously reported alkylation (Ph/sub 2/PCH/sub 2/CH/sub 2/PPh/sub 2/)/sub 2/W(CO)(CS) + MeOSO/sub 2/F ..-->.. (Ph/sub 2/PCH/sub 2/CH/sub 2/PPh/sub 2/)/sub 2/W(CO)(CSMe)/sup +/SO/sub 3/F/sup -/ (1), and Lewis adduct formation reactions of terminal CS groups in electron-rich complexes presumably also yield CSR carbyne complexes. These results suggest that similar adducts of terminal CO ligands could be reasonable intermediates in catalytic reactions of carbon monoxide which lead to the cleavage of the carbon-oxygen triple bond. A single crystal of (eta-C/sub 5/H/sub 5/)W(PPh/sub 3/)(CO)(CSPh) approx. 0.2 x 0.15 x 0.4 mm was chosen for the x-ray diffraction study. The average distance from the tungsten to the cyclopentadienyl carbon atoms is 2.366 A. Data were given for the other ligands. 1 figure. (DP)

• Research Organization: Iowa State Univ., Ames
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 5773546
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 101:25; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKENES
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
CYCLOALKENES
CYCLOPENTADIENE
DIENES
DIFFRACTION
HYDROCARBONS
LIGANDS
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
ORGANIC SULFUR COMPOUNDS
POLYENES
SCATTERING
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES
X-RAY DIFFRACTION