Advances in Physical Organic Chemistry, Vol. 23 by D. Bethell (ed.)

By D. Bethell (ed.)

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In the presence of a large excess of [(q5-C,H,)Mo(CO),]-, compound [14] is produced, presumably by a pathway analogous to that shown in Scheme 17. co -MO’ 1 ’co ~ 4 1 This proposed mechanism is further reinforced by the formation of the heterobimetallic species of the structure shown in [ I 51 formed from the reaction between [(q’-C,H,)W(CO),]and [(q5-C,H,)Mo{(CH,),Br}(CO),]. However, here the carbene is unexpectedly coordinated to the tungsten atom. , 1975). Poo oc.... oc‘ A. I0 C w \% ’ ~ 5 1 46 SUNDUS HENDERSON AND RICHARD A.

Consistent with these observations, when the reaction between trans-[IrBr(CO)(PMe,Ph),] and C,H,Cl is performed in the presence of an excess of LiBr, only one product is obtained, which contains no Ir-CI bonds (Pearson and Poulos, 1979). trans-[IrBr(CO)(PMe,Ph),l + C1- trans-[IrCI(CO)(PMe,Ph),] + Br(28) 36 SUNDUS HENDERSON AND RICHARD A. HENDERSON The addition of acyl halides to trans-[IrCI(CO)(PMe,Ph),] also occurs with a trans-stereochemistry as shown in (29) (Deeming and Shaw, 1969; Kubota and Blake, 1971; Collman and Sears, 1968).

The alkylation of the dicobalt anion with a,y-diiodides occurs with a complicated stereochemistry as evidenced by the studies with mesoand (f)-2,4-dimethylpentane. The mechanism of the reaction is shown in Scheme 8. The initial alkylation occurs with complete loss of stereochemical FI - /c\ cpco=cocp ‘c’ + yy H 6 I c7 cpco=cocp k I + ‘c’ H I (A) d cpco- cocp I ’ \\ &’ $ 0 0 Scheme 8 c;co-c~cp 1’1 $ $ 0 0 30 SUNDUS HENDERSON AND RICHARD A HENDERSON integrity as a consequence of an electron-transfer process.

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