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

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Olefin)( q2-alkyne)ML, dn orbital splitting pattern. (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).

9). The W(C0)2(HOC=CC6H4Me)(acac)c1 product of carbyne-carbonyl coupling is one of few examples of a structurally characterized dicarbonyl alkyne d 4 monomer (100). Details of the geometry of the tungsten dicarbony1 alkyne fragment were not published in the original aommunication, and further work with two 7~ acids adjacent to an alkyne ligand is required to assess general geometric properties of such moieties. c. CpML(RC=CR)X The metal-alkyne bonding parameters of molecules of the type CpML(RC=CR)X are similar to those of other classes of four-electron donor alkynes in Table I.

2000 1675* 2050. 200s 4Y 51 51 1690 51 204s. I990 I620 ' I978 2060. IYhIJ 167S* Mo(CO)(PhC=CPh)( MeCN),I, W(CO),( HOC=CC,H,Me)(acac)CI 51 100 (W=CHPh)(PhC=CPh)(PMe3),CIZ [W(CNBu'),(RHNC=CNHR)I]I 223 I82 [Mo(CNBu'),( Bu'HNC=CNHBu')l]I 193 [Mo(CNBu'),(Bu'HNC=CNHBu')Br] . ](CO)( PEt,)W( MeOC=CSMe)}[FSO,] 23 1 . NC=CMe)( S,CNMe,): 1920 1908 217 218 W(CO)(PhC=CPh)(S,CNEt2)2 W(CO)(HOCH2C=CCHZOH)(S,CNEt2)2 W(C0)(Et,NC=CMe)(SZCNEt,), W(CO)(MeC=CMe)(S2CNEt,), W(CO)(E tC=CEt)(S,CNEt,), W(CO)(DMAC)(S,CNEtz): W(CO)(r-cyclooctyne)(S2CNEt2), W(CO)( r-cyclooctyne)( S2CNMeJ2 214 21s W(CO)(Ph2PC=CPPh2)(S2CNEt2), W(CO)(PhC=COMe)( C,H,N2)?

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