By F.G.A. Stone, Robert West (Eds.)
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Extra info for Advances in Organometallic Chemistry, Vol. 29
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. The tungsten-to-alkyne carbon bond distances change only slightly (Table I), but the orientation of the alkyne in the mixed olefin alkyne complex is rotated 90” relative to the carbonyl case.
These ligands should not be crowded by the cis alkyne, which lies perpendicular to the La,-M-L,, axis, and in either an idealized octahedral or idealized seven-coordinate formalism these two ligands adopt an angle of 180" relative to one other. In the same way that terminal 0x0 or nitrene units create a pyramidal distortion in M(0)L5 (131) and M(NR)L5 (132) complexes, alkynes also tend to pull the metal out of the plane of the four adjacent ligands. 4. Trigonal bipyramidal Mo(HC=CH)(CNBU~)~(SB'), geometry.
10. Alkyne orientations in d4 CpMo(CO)(CF3C~CCF3)(sc6F~) and d 2 CpMo(0) (CF~CECCF~)(SC~FS). Alkyne orientation in these complexes depends on the two cis ligands. An early comparative structural study of CpMo(CO)(CF3C-CCF3)(SC6F5) and CpMo(0)(CF3C=CCF,)(SC6F5) which revealed alkyne orientations differing by 90" for the d 4 and d 2 configurations (Fig. 10) was important in elucidation of electronic factors dictating alkyne rotational preferences (135). All of the d 4 CpM(CO)(RC=CR)L examples in Table I have the alkyne aligned parallel to the single M-CO axis.
Advances in Organometallic Chemistry, Vol. 29 by F.G.A. Stone, Robert West (Eds.)