Coupling of cyclooctyne with carbon monoxide on divalent molybdenum and tungsten. Crystal and molecular structure of a bis(hexamethylene)cyclopentadienonetungsten complex, W(S2CNMe2)2(CO){(C8H12)2CO}

Bennett, Martin A., Boyd, Ian W., Robertson, Glen B. and Wickramasinghe, Wasantha A. (1985) Coupling of cyclooctyne with carbon monoxide on divalent molybdenum and tungsten. Crystal and molecular structure of a bis(hexamethylene)cyclopentadienonetungsten complex, W(S2CNMe2)2(CO){(C8H12)2CO}. Journal of Organometallic Chemistry, 290 2: 181-197.


Author Bennett, Martin A.
Boyd, Ian W.
Robertson, Glen B.
Wickramasinghe, Wasantha A.
Title Coupling of cyclooctyne with carbon monoxide on divalent molybdenum and tungsten. Crystal and molecular structure of a bis(hexamethylene)cyclopentadienonetungsten complex, W(S2CNMe2)2(CO){(C8H12)2CO}
Journal name Journal of Organometallic Chemistry   Check publisher's open access policy
ISSN 0022-328X
1872-8561
Publication date 1985
Sub-type Article (original research)
DOI 10.1016/0022-328X(85)87431-3
Volume 290
Issue 2
Start page 181
End page 197
Total pages 17
Place of publication Lausanne, Switzerland
Publisher Elsevier
Language eng
Formatted abstract Cyclooctyne (C8H12) in excess reacts with the dialkyldithiocarbamato complexes M(S2CNR2)2(CO)2 (R = Me, Et; M == Mo, L = PPh3; M = W, L = CO, PPh3) to give a mixture of two complexes, M(S2CNR2)2)(CO){(C8H12)2CO} (1-4) and M(S2CNR2)2(C8H12){(C5H12)2CO} (5-8). These contain tetrahapto-bis-(hexamethylene)cyclopentadienone, (C8H12CO, formed by the condensation of two molecules of cyclooctyne with one molecule of CO. Crystals of W(S2CNMe2)2(CO){(C8H12)2CO} (3) are monoclinic, space group P21/n, with a 15.132(1), b 15.705(2), c 11.346(1) Å, β 93.68(2)°, and Z = 4. The structure was solved by heavy-atom methods and refined by least-squares methods to R = 0.027 (Rw = 0.045) for 5811 unique data [I ≧ 3σ(I)]. The molecule is approximately pentagonal bipyramidal, with terminal CO and one sulphur atom of a bidentate Me2NCS2 ligand in the axial positions. The equatorial sites are occupied by the other sulphur atom of this Me2NCS2 ligand, the second bidentate Me2NCS2 ligand, and the mid-points of the coordinated CC bonds of η4-(C8H12CO. As in other cyclopentadienone complexes, the CC distances in the η4-dienone are almost equal (av. 1.45 Å) and the CO group is bent away from the plane of the ring (dihedral angle 17.6°). Infrared and NMR (1H, 13C) data suggest that complexes 5-8 are similar to 1-4, with cyclooctyne acting as a 2π-electron donor in place of CO.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ

Document type: Journal Article
Sub-type: Article (original research)
Collection: National Research Centre for Environmental Toxicology Publications
 
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