Download Advances in Organometallic Chemistry, Vol. 29 by F.G.A. Stone, Robert West (Eds.) PDF

By F.G.A. Stone, Robert West (Eds.)

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By F.G.A. Stone, Robert West (Eds.)

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Extra resources for Advances in Organometallic Chemistry, Vol. 29

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03 A) indicate multiple bond character. rr orbital. Recognition that the C=C bond length is not a sensitive indicator of alkyne nl donation was also an important general point noted by McDonald and co-workers (57). Secondary features such as W-S bond distances reflect the trans influence of the carbonyl and alkyne ligands as well as variable 7~ bonding from the dithiocarbamates to the tungsten as a function of metal drr orbital occupancies (134). Comparison of the structures of W(CO)(HC=CH)(S2CNEt2)2 (57) and W(MA)(PhC=CH)(S,CNEt,), (60) indicates that major changes accompany replacement of carbon monoxide with a single-faced wacid olefin ligand.

8. Octahedral W(MA)(HC=CPh)(S2CNMe2)2 geometry. 30 FIG. 9. W-L CPh)(CsHJ'J&. JOSEPH L. TEMPLETON bond lengths in W(CO)(HC=CH)(S2CNEt,)2 and W(CO)(MeOC- Structures of other alkyne complexes containing chelating ligands have been reported for products derived from carbyne-carbonyl coupling reactions. The Schiff base pyrrole-2-carboxaldehydemethyliminehas been used to generate anionic v2-ketenyl products, and the methylated alkyne analog then belongs to the class of bisbidentate carbonyl alkyne d4 monomers.

Vacant n* orbitals of the two single-faced wacid C2ligands stabilize dxy (rrll*) and d,, (n*)which house the four metal electrons. In the idealized ethylene-acetylene model complex the HOMO1 is the olefin stabilized d,, while the HOMO2 orbital, dxY,reflects alkyne nil* overlap. The M-C alkyne distances employed in the calculation increase overlap responsible for the alkyne-metal T interactions relative to the olefin which is further from the metal and overlaps less (60). The d n bonding contribution of the single-faced n-acid olefin is to stabilize the lone filled drr orbital which is independent of the alkyne.

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