By F.G.A. Stone, Robert West (Eds.)
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60). The ground state geometry produces a LUMO consisting of dyr destabilized by nl donation; the alkyne is a four-electron donor. 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).
Mo(PhC=CPh)(SBu'),(CNBu')2 Cp2W(MeCECMe) Cp,Mo( CF,C=CCF,) ( qF-C5H4Me)2Mo(CF3C=CCFx) 227, 223. 231, 229, 198 195 227, 226. 228, 227. 223, 227. 192 200 201 192 197 198 1 I5 I83 I95 194 v(CO)," cm-' 2001 1720* 167Y l650* 1690* I665 * 1675* I 6JO* 1678' lh78* 1962 I968 1975 1951 1975 1976 1970 1975 I070 Ref. 5 107 107 107 1975 I970 1975 1771* 1830* 1755* 1750* 1782* 1778' ION I ON IOX 85 x5,155 133 85 x5 12x "Compounds for which the v(C=C) frequency has been reported are included with an asterisk to indicate this value.
4). In other words the alkyne points along the r-acid axis as usual in d 4 monomers. The presence of two thiolates in the equatorial belt provides additional r-donor electrons for this unsaturated d4 complex as described in the molecular orbital section which follows. 06 A are on the high end of the four-electron donor range and probably reflect r-donor competition with thiolate lone pair electrons. Another important six-coordinate alkyne derivative with monodentate ligands which has been structurally characterized is W(=CHPh)(PhC=CPh)(PMe3)2C12 (78).
Advances in Organometallic Chemistry, Vol. 29 by F.G.A. Stone, Robert West (Eds.)