SYNTHESIS, STRUCTURE, AND FLUXIONAL BEHAVIOR OF OCTAHEDRAL RUTHENIUM(II) COMPLEXES WITH MIXED OXYGEN PHOSPHINE-LIGANDS - P-31 DNMR SPECTROSCOPIC STUDIES, LINE-SHAPE ANALYSIS, AND DETERMINATION OF REARRANGEMENT BARRIERS

The synthesis and spectroscopic properties of ether-phosphine ruthenium(II) complexes of the type Cl2Ru(P small cap O)2 (5a, 7a-10a) and trans-Cl2Ru(CO)(P approximately O)(P small cap O) (5b, 7b-10b) are reported. Temperature-dependent P-31 NMR spectra of the fluxional complexes 1b-11b and cis-Cl2Ru(CO)(P approximately O)(P small cap O) (1c-3c) were measured and by using a modified version of DNMR5, computer-generated spectra were obtained and fitted to the experimental spectra. Graphic application of the Eyring equation to the kinetic data afforded the thermodynamic parameters DELTAH(double dagger), DELTAS(double dagger), and DELTAG(double dagger). Complex 11b with the strong basic four-membered ether-phosphine 11 crystallizes in the monoclinic space group P2(1)/n, with a = 11.974(2) angstrom, b = 10.877(2) angstrom, c = 29.567(6) angstrom, beta = 96.34(3)-degrees, Z = 4, and V = 3827.2(12) angstrom3 (R = 0.075 and R(w) = 0.076).