Advances in Organometallic Chemistry, Vol. 29 by F.G.A. Stone, Robert West (Eds.)

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

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Example text

13 8, for L = CO. The only other cyclopentadienyl derivative included in the bisalkyne structural data is an unusual tungsten acetylide which is 7~ bound to a CpW(HC=CPh)(CO) fragment (138). The net result can effectively be considered a mixed bisalkyne monomer. The geometry of M O ( M ~ C = C M ~ ) , ( S ~ C N C , His~ )octahedral ~ (88). The two alkynes are cis and parallel (Fig. 13), reminiscent of the olefinalkyne structure found for W(MA)(PhC=CH)(S,CNEt,),. The cis-bent angle CEC-Me angle of 146" is typical of alkyne ligands.

143 134. 28 136,145 148,152 139. 140 81 - 138. 06. 99. 30 26 JOSEPH L. 3. Octahedral Mo(CO)(PhC=CH)(PEt3)ZBrZgeometry. tightly bound four-electron donor alkynes. The ancillary ligands in Mo(CO)(PhC=CH)(PEt3),Br2 adopt a trans-phosphine-cis-bromide arrangement as shown in Fig. 3. The Lewis acid-oxygen adduct which serves as a ligand in W(C0)( H C Z C O A I C ~ ~ ) ( P M ~ ~can ) ~ Cprofitably I be viewed as an alkyne bound to tungsten(I1) (101). 32 A, is indeed cis to CO and lies parallel to the W-CO axis.

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.

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