PREPARATION AND STRUCTURES OF 2 STERICALLY PROTECTED RUTHENIUM PORPHYRIN COMPOUNDS OF THE TYPE-RU(POR)(H2O)(IN)(CO)(OUT)

Two sterically protected ruthenium porphyrin compounds of the type Ru( Por)(H2O)in(CO)out have been prepared, and their structures have been determined by single-crystal X-ray diffraction methods. Both compounds , Ru(beta-PocPivP)(H2O)in(CC)out (1), a ''pocket'' porphyrin, and Ru(O CCOPor)(H2O)in(CO)out (2), a ''capped'' porphyrin, pack as discrete po rphyrin units with solvate molecules. In both compounds, the H2O ligan d is inside the sterically protected region while the CO ligand is tra ns to the H2O molecule and is on the outside of the protected region. In Ru(beta-PocPivP)(H2O)in(CO)out, the H2O ligand is hydrogen-bonded t o an amide oxygen atom, the O(H2O)-O(amide) distance being 2.688(4) an gstrom; in Ru(OCCOPor)(H2O)in(CO)out, the H2O ligand, though not invol ved in traditional hydrogen bonding, may interact with the aromatic pi system of the benzene cap, the O(H2O)-cap centroid distance being 2.9 8 angstrom. The carbonyl groups have their normal, linear arrangement, with the Ru-C-O angles being 178.7(3) and 178.1(4)degrees in 1 and 2, respectively. In each structure, the porphyrin plane is slightly ruff led, with the Ru atom lying 0.20 and 0.26 angstrom below the porphyrin plane toward the carbonyl group in 1 and 2, respectively. In each str ucture, the cap is off-center and tilted. Each cap centroid lies 4.25 (1) and 4.79 A (2) above the porphyrin plane. These structures provide some useful insights info steric constraints in these encumbered porp hyrins. Crystallographic data for Ru(beta-PocPivP)(H2O)in(CO)out.2CHCl 3 (1): triclinic, C(i)l-P1BAR, Z = 2, a = 13.261(3) angstrom, b = 14.4 50(3) angstrom, c = 15.716(3) angstrom, alpha = 91.63(3)degrees, beta = 94.94(3)degrees, gamma = 94.40(3)degrees, 1 = -167-degrees-C, 11 611 unique reflections, 805 variables, R(F( (F(o))2 > 2sigma(F(o)2)) = 0. 045, R(w)(F2) = 0.101. Crystallographic data for Ru(OCCOPor)-(H2O)in(C O)out-2CHCl3-1/2n-C6H12 (2): triclinic C(i)l-P1BAR, Z = 2, a = 9.651(2 ) A, b = 11.936(2) angstrom, c = 25.964(5) angstrom, alpha = 92.14(3)d egrees, beta = 91.58(3)degrees, gamma = 104.99(3)degrees, t = -167-deg rees-C, 15 970 unique reflections, 760 variables, R(F) (F(o)2 > 2sigma (F(o)2)) = 0.086, R(w)(F2) = 0.183.