X-ray structures of trans-dichloro(4-methylphyrimidine) (#eta#~1-phenyl)bis(pyridine)rhodium(III) hydrate and trans-dichloro(phenyl)tris(triphenylstibine)rhodium(III) ethylacetate solvate. Molecular orbital analysis of trans-dichloro (4-methylpyrimid

摘要

The crystal and molecular structure of trans-dichloro(4-methylpyrimidine)(#eta#~1-phenyl)cis-bis(pyridine)rhodium(III) water solvate, 1 * 0.17H_2O, and trans-dichloro(#eta#~1-phenyl)tris(triphenylstibine)rhodium(III) ethylacetate solvate, 2 * CH_3CO_2CH_2CH_3 have been studied via X-ray diffraction from a single crystal at room temperature. The final refinement converged to R1 conventional index of 0.0350 and 0.0361 for the structural analysis of 1 * 0.17H_2O [space group R(-3)] and 2xCH_3CO_2CH_2CH_3 [P(-1)], respectively. The 4-methylpyrimidine ligand (Pym) is only weakly bound to Rh in 1, as shown by the long Rh-N distance (2.251(4) A), compared to the Rh-N(pyridine) lengths [average, 2.066(4)]. N-C bond distances involving the N donor average 1.329(6) and 1.345(6) for Pym and pyridine (Py) ligands, respectively. The C-N-C bond angle on the donor is 114.1(5) deg for Pym and average 117.4(4) deg for Py. The structure of the complex molecule of 2xCH_3CO_2CH_2CH_3 has some differences when compared to that of the corresponding acetone solvate previously studied in this laboratory (Cini, R., Giorgi, G, and Pasquini, L., Inorg, Chim. Acta, 1992, 196, 7). The two structures differ mainly by the orientation of the phenyl donor with respect to the Cl-Rh-Cl axis (which is more eclipsed for the ethylacetate solvate) and by the conformation of the SbPh_3 ligands. Density functional calculations at the B3L YP/LANL2DZ level with full geometry optimization were carried out on the free Pym molecule and on some Sc(N~1-Pym)~(3+) and Sc(N`2-Pym)~(3+) model molecules. The effect of metal coordination consists mainly in enlarging the (Sc)N-C bond distances up to 0.150 A, whereas the C-N(Sc)-C bond angle decreases of 1.9 deg. Significant changes on other bond lengths and angles relevant to ring atoms of Pym occur upon metal coordination to the nitrogen atom. The metal coordination to N(2) is less favorable than to N(1) of 7.5 kcal for 1:1 species of Sc~(3+). Extended Huckel calculations showed that HOMO consists mostly of metal-d orbitals with some character of chloride and phenyl and pyrimidine ligands, whereas LUMO is composed of phenyl, pyridine and pyrimidine orbitals. The method well reproduces the Rh-N and Rh-C bonding distances and gives Rh-C dissociation energy 2.38 and 5.48 times that for the Rh-N(Py) and Rh-N(Pym) bonds, respectively.