Isocyanide-substituted Re alkyl complexes cis-p-XC(6)H(4)CH(2)Re(CO)(4
)(CN-p-tolyl) (X = Cl, OMe) were prepared from the PdO-catalyzed react
ion of p-XC(6)H(4)CH(2)Re(CO)(5) (X = Cl, OMe) with p-tolyl isocyanide
. On heating in toluene these complexes undergo isocyanide insertion i
nto the Re-C bond to afford iminoacyl complexes which further react to
orthometallate the p-tolyl ring. An X-ray crystal structure determina
tion on (CO)(4)Re(C6H3(CH3))N(H)=CCH(2)C(6)H(4)p-Cl (3a) revealed that
C19H13ClO4NRe crystallizes in the monoclinic space group P2(1)/c with
4 formulas per unit cell. Unit cell parameters are a = 9.799(1), b =
15.252(2), c = 13.569(2) Angstrom and beta = 110.788(8)degrees. The st
ructure shows Re-C bond distances indicative of substantial carbenoid
character.