The reactions of five Schiff bases (SB), viz.,N,N′- ethylenebis ( p-tolualideneimine) (SB 1),N,N′-ethylenebis( p-N,N- dimethylaminobenzalideneimine (SB 2), N,N′- ethylenebis (cinnamylideneimine) (SB 3), N,N′-ethylenebis(methyl- p -methoxyphenylketimine) (SB 4) and N,N′-ethylenebis(methyl- p-methylphenylketimine) (SB 5), with group VI metal carbonyls in aromatic hydrocarbon solvents have been studied. Mo(CO) 6 and W(CO), invariably gave cis-[(SB)M(CO) 4] (M = Mo and W) derivatives but Cr(CO) 6 yielded a mixture of [(SB)Cr(CO) 4] and the appropriate (arene)chromium tricarbonyl for SB = SB 1, SB 2 and SB 4 and the only (arene)chromium tricarbonyl for SB = SB 3 and SB 5. [M(CO) 5(Ph 3P)] (M = Cr and Mo) after reaction with SB give SB-bridged dinuclear [(Ph 3P)(CO) 4M(μ-SB) M(CO) 4(Ph 3P)] derivatives. Nitrosylation of cis-[(SB)M(CO) 4] (M = Cr and Mo) using NO-swept benzene has also been performed.