Exploration of Solid-State vs Solution-State Structure in Contact Ion Pair Systems: Synthesis, Characterization, and Solution-State Dynamics of Zinc Diphenyl Phosphate, [Zn{O2P(OPh)2}2], Donor- Base-Supported Complexes

A family of zinc phosphate complexes supported by nitrogen donor-base ligands have been synthesized, and their molecular structures were identified in both the solid (X-ray crystallography) and solution state (DOSY NMR spectroscopy). [Zn{O2P(OPh)2}2]infinity (1), formed from the reaction of Zn[N(SiMe3)2]2 with HO(O)P(OPh)2 coordinates to donor-base ligands, i.e., pyridine (Py), 4-methylpyridine (4-MePy), 2,2bipyridine (bipy), tetramethylethylenediamine (TMEDA), pentamethyldiethylenetriamine (PMDETA), and 1,3,5-trimethyl-1,3,5triazacyclohexane (Me3-TAC), to produce polymeric 1D structures, [(Py)2Zn{O2P(OPh)2}2]infinity (2) and [(4-MePy)2Zn{O2P-(OPh)2}2]infinity (3), the bimetalic systems, [(Bipy)Zn{O2P(OPh)2}2]2 (4), [(TMEDA)Zn{O2P(OPh)2}2]2 (5), and [(Me3-TAC)Zn-{O2P(OPh)2}2]2 (7), as well as a mono-nuclear zinc bis-diphenylphosphate complex, [(PMDETA)Zn{O2P(OPh)2}2] (6). 1H NMR DOSY has been used to calculate averaged molecular weights of the species. Studies are consistent with the disassembly of polymeric 3 into the bimetallic species [(Me-Py)2 center dot Zn2{O2P(OPh)2}4], where the Me-Py ligand is in rapid exchange with free Me-Py in solution. Further 1H DOSY NMR studies of 4 and 5 reveal that dissolution of the complex results in a monomer dimer equilibrium, i.e., [(Bipy)Zn{O2P(OPh)2}2]2 2[(Bipy)Zn{O2P(OPh)2}2] and [(TMEDA)Zn{O2P(OPh)2}2]2 2[(TMEDA)Zn{O2P(OPh)2}2], respectively, in which the equilibria lie toward formation of the monomer. As part of our studies, variable temperature 1H DOSY experiments (223 to 313 K) were performed upon 5 in d8-tol, which allowed us to approximate the enthalpy [Delta H = -43.2 kJ mol-1 (+/- 3.79)], entropy [Delta S = 109 J mol-1 K-1 (+/- 13.9)], and approximate Gibbs free energy [Delta G = 75.6 kJ mol-1 (+/- 5.62) at 293 K)] of monomer-dimer equilibria. While complex 6 is shown to maintain its monomeric solid-state structure, 1H DOSY experiments of 7 at 298 K reveal two separate normalized diffusion coefficients consistent with the presence of the bimetallic species [(TAC)2-xZn2{O2P(OPh)2}4], (x = 1 or 0) and free TAC ligand.