Syntheses, structures, and reactivities of novel palladium beta-diiminato-acetate complexes.
The reaction between (Ar(2)nacnac)H (Ar = C(6)H(5), ligand a; 2,6-((i)Pr)(2)C(6)H(3), ligand b) and [Pd(OAc)(2)] produces red complexes [Pd(Ar(2)nacnac)(OAc)] (1a: Ar = C(6)H(5); 1b: Ar = 2,6-((i)Pr)(2)C(6)H(3)). Complex 1a has a dimeric structure in the solid state with two bridging acetates, while a monomer-dimer equilibrium establishes in solution. Complex 1b is monomeric in both the solid state and solution. Both are air- and moisture-stable compounds, unlike [Pd(Ph(2)nacnac)(2)] (2), which easily hydrolyzes in the presence of moisture to give [Pd(Phnacac)(2)] (3) (Phnacac = {CH(3)C(NPh)CHC(O)CH(3)}(-)). Compound 1a reacts with metal acetates to produce heterotrimetallic complexes of a general formula [Pd(Ph(2)nacnac)](2)-mu-[M(OAc)(4)] (4, M = Cu; 5, M = Zn). Treating 1a with KOH in THF, or alternatively [Pd(Ph(2)nacnac)Cl](2) with KO(t)Bu in wet THF, produces [Pd(Ph(2)nacnac)(OH)](2) (6).
Hadzovic
Alen
A
Davenport Chemical Research Laboratories, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, Canada, M5S 3H6.
Song
Datong
D