Amido phosphine complexes of zinc: synthesis, structure, and catalytic ring-opening polymerization of epsilon-caprolactone

A series of diarylamido phosphine ligands of the type N-(2-dihydrocarbylphosphinophenyl)-2,6-dialkylanilide 1a-d have been prepared and employed to investigate the coordination chemistry of zinc. Protonolysis of ZnMe(2) with one equivalent of N-(2-diphenylphosphinophenyl)-2,6-dimethylaniline (H[1a]) produced a mixture of [1a] ZnMe (2a) and Zn[1a](2) (4a), whereas that involving ZnEt(2) gave exclusively the three-coordinate [1a] ZnEt (3a). In contrast, treatment of ZnR(2) (R = Me, Et) with N-(2-diphenylphosphinophenyl)-2,6-diisopropylaniline (H[1b]), N-(2-diisopropylphosphinophenyl)2,6- dimethylaniline (H[1c]), or N-(2-diisopropylphosphinophenyl)-2,6-diisopropylaniline (H[1d]) under similar conditions generated quantitatively the corresponding three-coordinate zinc methyl 2b-d and zinc ethyl 3b-d. The bis-ligand complexes 4a, b, d were isolated by either protonolysis of alkyls 2-3 with one equivalent of H[1] or metathesis of ZnX(2) (X = Cl, OAc) with the corresponding lithium derivatives 5. Attempts to prepare [1a-d]ZnX (X = Cl, OAc) were not successful regardless of stoichiometry of the starting materials employed. Alcoholysis of zinc alkyls 2-3 led undesirably to protonation on the amido nitrogen donor of 1, highlighting perhaps its higher basicity than alkyls. The reaction of ZnCl(2) with H[1c] generated the phosphorus-bound adduct {H[1c]ZnCl(mu-Cl)}(2) (6c). Interestingly, attempts to deprotonate 6c with n-BuLi produced unexpectedly the alkylated product [1c] Zn(n-Bu) (7c) instead of [1c] ZnCl; analogous reactions employing NEt(3) led to Lewis base substitution to give H[1c] and [ZnCl(2)(NEt(3))](2). Structural characterization of all new compounds was achieved by multi-nuclear NMR spectroscopy ((1)H, (13)C, (31)P, and (7)Li) and X-ray crystallography (2c-d, 3c, 4d, 5c-d, and 6c) where appropriate. On the basis of the NMR and X-ray data, in combination with the synthetic investigations, the steric nature of these amido phosphine ligands is recognized to follow the order of 1a < 1b < 1c < 1d. Interestingly, zinc alkyls 2-3 are all active initiators for catalytic ring-opening polymerization of epsilon-caprolactone whereas the bis-ligand complexes 4 are not.