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

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Extra info for Advances in Organometallic Chemistry, Vol. 29

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A single rigid isomer with I and L trans to the two cis-CO ligands, respectively, could give the observed 'H spectrum. Alternatively, two isomers with rotating alkynes could give the observed 'H spectrum. In one isomer both I ligands could be trans to carbonyls, in the other one I could be trans to alkyne (Fig. 19). 1 kcal/mol are found for cis-WL,(CO)(MeC=CMe)Br, with L = CNBu' and PPh3, respectively. The coalescence temperature of -14°C for L = P(OMe)3 (48) allows an estimate of AG* of 12-13 kcal/mol for the cis-P(OMe)3 isomer.

The alkyne then lies parallel to this axis in order to enjoy backbonding into the T I , *orbital while confronting a pair of vacant metal orbitals of idealized e’ symmetry (largely dxy and dX2+) in the xy plane to serve as acceptors for nl donation (Fig. 20). The two thiolates are also equatorial ligands, and they have their R groups in anti-upright orientations so that both sulfur atoms can also donate electron density from filled lone pair p orbitals to the metal e’ orbitals in the xy plane (133).

Substitution of one carbonyl ligand eliminates the symmetry plane and has a dramatic impact on d r orbital combinations and orientational preferences as described in a companion paper by Schilling, Hoffmann, and Faller (146). In fact monocarbonyl alkyne derivatives have been more thoroughly investigated than any other class of d4 alkyne complex, and we now turn to the alkyne alignment which is easily understood in the context of d r orbital occupancies as dictated by a single cis carbonyl ligand.

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