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

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W(=CHPh)(PhC=CPh)(PMe&C12 geometry. Several structures of coupled isonitrile alkyne complexes are available. Variations among the cation geometries are small for [Mo(B~'NHC=CNHBU')(CNBU')~X]'with X = Br, I, or CN (229). The cationic bipyridine complex also displays similar diaminoalkyne parameters (218). 05 8, are found with bend back angles of 128-130". 40 8, are uniformly longer than those of other d 4 alkyne adducts, presumably reflecting the delocalized T system involving both planar nitrogens, the alkyne carbons, and the d4 Mo2+ ion.

A secondary feature of the cis-M(CO)(RC=CR) molecular orbital description is the three-center-two-electron bond built from carbonyl r Y * , alkyne T I I *and , metal dyr (Fig. 15) (45). EHMO calculations locate the completely in-phase bonding combination, dominated by d,,, approx- -L O S E - DRAW X 3t- FIG. 15. Three-center-two-electron bond in L,M(CO)(RC=CR) complexes. 4 eV below the HOMO which consists of d,, stabilized by CO rrx*. The three-center bond is redundant in terms of rr-acid stabilization of dyz, and indeed replacement of the carbonyl ligand with a singlefaced rr-acid olefin or carbene to create complexes with three simple two-center-two-electron drr-ligand rr bonds has been achieved.

The r-ligand properties of the PMe, ligands are probably not sufficiently dominant to create a substantial alkyne preference between the d r orbital combinations which are available. 11. [($-C9H7)Mo(MeC~CMe)(PMe3)2]+ geometry. 32 JOSEPH L. The impact of this m-donor role for the vl-ketenyl ligand on the cis-alkyne geometry is minimal as the aminoalkyne ligand structural parameters fall in the range typical of four-electron donor alkynes. i ii The first olefin-alkyne Group VI d4 complex to be structurally characterized contained a coordinated vinyl ligand which was part of a styrene attached to a metal-bound phosphine (136).

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