Rh(II) and Rh(I) two-legged piano-stool complexes: structure, reactivity, and electronic properties.

The ligand 1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene, 3, was used to synthesize a mononuclear Rh(II) complex [(eta(1):eta(6):eta(1)-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh][PF(6)](2), 6+, in a two-legged piano-stool geometry. The structural and electronic properties of this novel complex including a single-crystal EPR analysis are reported. The complex can be cleanly interconverted with its Rh(I) form, allowing for a comparison of the structural properties and reactivity of both oxidation states. The Rh(I) form 6 reacts with CO, tert-butyl isocyanide, and acetonitrile to form a series of 15-membered mononuclear cyclophanes [(eta(1):eta(1)-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh(CO)(3)][PF(6)] (8), [(eta(1):eta(1)-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh(CNC(CH(3))(3))(2)][PF(6)] (10), and [(eta(1):eta(1)-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh(CO)(CH(3)CN)][PF(6)] (11). The Rh(II) complex 6+ reacts with the same small molecules, but over shorter periods of time, to form the same Rh(I) products. In addition, a model two-legged piano-stool complex [(eta(1):eta(6):eta(1)-1,4-bis[3-(diphenylphosphino)propoxy]-2,3,5,6-tetramethylbenzene)Rh][B(C(6)F(5))(4)], 5, has been synthesized and characterized for comparison purposes. The solid-state structures of complexes 5, 6, 6+, and 11 are reported. Structure data for 5: triclinic; P(-)1; a = 10.1587(7) A; b = 11.5228(8) A; c = 17.2381(12) A; alpha = 96.4379(13) degrees; beta = 91.1870(12) degrees; gamma = 106.1470(13) degrees; Z = 2. 6: triclinic; P(-)1; a = 11.1934(5) A; b = 12.4807(6) A; c = 16.1771(7) A; alpha = 81.935(7) degrees; beta = 89.943(1) degrees; gamma = 78.292(1) degrees; Z = 2. 6+: monoclinic; P2(1)/n; a = 11.9371(18) A; b = 32.401(5) A; c = 12.782(2) A; beta = 102.890(3) degrees; Z = 4. 11: triclinic; P(-)1; a = 13.5476(7) A; b = 13.8306(7) A; c = 14.9948(8) A; alpha = 74.551(1) degrees; beta = 73.895(1) degrees; gamma = 66.046(1) degrees; Z = 2.

Out-of-center distortions in d(0) transition metal oxide fluoride anions.

Electronic effects and the bond network are the two factors that cause out-of-center distortions in octahedral d(0) transition metal oxide fluoride anions. Overlap between filled oxide p orbitals and vacant cation d orbitals results in strong, short metal-oxide bonds causing the metal ion to distort toward the oxide ligand. This primary, electronic distortion is not dependent on the extended structure. Smaller, secondary distortions of the anionic octahedra are caused by interactions with the bond network. [HNC(6)H(6)OH](2)[Cu(NC(5)H(5))(4)(NbOF(5))(2)], prepared with 5-hydroxy-2-methylpyridine that provides two coordination contact sites to the anion when protonated, exhibits distortions in the anion reflecting both factors. Crystal data for [HNC(6)H(6)OH](2)[Cu(NC(5)H(5))(4)(NbOF(5))(2)]: monoclinic, space group C2/c (No. 15), with a = 10.9427(8) A, b = 16.204(1) A, c = 21.396(2) A, beta = 93.263(1) degrees, and Z = 4. Conditions for detection of both distortion types are discussed with five additional examples.

Synthesis, structure, and theoretical study of the nonclassical [CuTe(7)](3-) anion.

The compound [PPh(4)](2)[NEt(4)][CuTe(7)] has been synthesized from the reaction of CuCl with a polytelluride solution in dimethylformamide at room temperature. The compound crystallizes with two formula units in the triclinic space group P(-)1 in a cell with dimensions a = 8.9507(18) A, b = 14.714(3) A, and c = 23.277(5) A and alpha= 86.32(3) degrees, beta= 80.17(3) degrees, and gamma= 75.63(3) degrees (T = -120 degrees C). Ab initio calculations indicate that the nonclassical [CuTe(7)](3)(-) anion is the result of joining Te(3)(2-) and [CuTe(4)](1-) fragments through donor-acceptor interactions.