Reaction of vinyl chloride with late transition metal olefin polymerization catalysts

The reactions of vinyl chloride (VC) with representative late metal, single-site olefin dimerization and polymerization catalysts have been investigated. VC coordinates more weakly than ethylene or propylene to the simple catalyst (Me(2)bipy)PdMe(+) (Me(2)bipy = 4,4'-Me(2)-2,2'-bipyridine). Insertion rates of (Me(2)bipy)Pd(Me)(olefin)(+) species vary in the order VC > ethylene > propylene. The VC complexes (Me(2)bipy)Pd(Me)(VC)(+) and (alpha-diimine)Pd(Me)(VC)(+) (alpha-diimine = (2,6-(i)Pr(2)bond]C(6)H(3))Ndouble bond]CMeCMedouble bond]N(2,6-(i)Pr(2)bond]C(6)H(3))) undergo net 1,2 VC insertion and beta-Cl elimination to yield Pdbond]Cl species and propylene. Analogous chemistry occurs for (pyridine-bisimine)MCl(2)/MAO catalysts (M = Fe, Co; pyridine-bisimine = 2,6-(2,6-(i)Pr(2)bond]C(6)H(3))Ndouble bond]CMe](2)-pyridine) and for neutral (sal)Ni(Ph)PPh(3) and (Pbond]O)Ni(Ph)PPh(3) catalysts (sal = 2-C(H)double bond]N(2,6-(i)Pr(2)-C(6)H(3))]-6-Ph-phenoxide; Pbond]O = Ph(2)PC(SO(3)Na)double bond]C(p-tol)O]), although the initial metal alkyl VC adducts were not detected in these cases. These results show that the L(n)MCH(2)CHClR species formed by VC insertion into the active species of late metal olefin polymerization catalysts undergo rapid beta-Cl elimination which precludes VC polymerization. Termination of chain growth by beta-Cl elimination is the most significant obstacle to metal-catalyzed insertion polymerization of VC.