A new class of supramolecular assemblies derived from a powerful Lewis acid in the form of dirhodium(II) tetra(trifluoroacetate) and various planar polycyclic aromatic hydrocarbons (PAHs) as donors has been prepared using a solventless technique. As a result, a number of novel adducts [Rh2(O2CCF3)4]x(L)y with various stoichiometries, x:y = 1:2, 1:1, 3:2, and 3:1, have been isolated in crystalline form. The following PAHs have been employed: acenaphthylene C12H8 (L1); acenaphthene C12H10 (L2); anthracene (L3) and phenanthrene (L4), C14H10; pyrene (L5) and fluoranthene (L6), C16H10; a series of isomers of the C18H12 composition: 1,2-benzanthracene (L7), triphenylene (L8), and chrysene (L9). Single-crystal X-ray diffraction studies have revealed a variety of structural motifs ranging from discrete molecules to extended 1D chains and 2D networks. In the bis-adducts, [Rh2(O2CCF3)4](L)2, an aromatic ligand is axially coordinated to the rhodium atoms through two long inequivalent Rh-C linkages at each end of the dirhodium complex. In the 1D complexes ([Rh2(O2CCF3)4](L))infinity aromatic ligands serve as bidentate links between two dirhodium units, while in 2D structures PAHs act as polydentate linkers, each coordinated to several rhodium atoms. Each linkage of a PAH consisted of an off-centered eta(2) coordination toward a single rhodium center. Simple Hückel calculations performed on the PAHs were used to calculate pi-electron densities for the C-C bonds, and these densities were compared to the experimental results.
The ambidentate character of dimethyl sulfoxide, already known for dirhodium carboxylates, has been remarkably manifested in new ways. Three novel complexes of dirhodium(II) tetra(trifluoroacetate) with the DMSO ligand, namely, [Rh2(O2CCF3)4]m(DMSO)n with m:n = 7:8 (1), 1:1 (2), and 3:2 (3), have been obtained by deposition from the vapor phase, and their crystal structures have been determined by X-ray crystallography. The crystallographic parameters are as follows: for 1, monoclinic space group P2(1)/c with a = 28.261(2) A, b = 16.059(4) A, c = 17.636(2) A, beta = 92.40(4) degrees, and Z = 2; for 2, triclinic space group P1 with a = 8.915(2) A, b = 10.592(2) A, c = 11.916(2) A, alpha = 84.85(1) degrees, beta = 88.86(1) degrees, and gamma = 65.187(8) degrees, and Z = 2; and for 3, triclinic space group P1 with a = 8.876(2) A, b = 9.017(2) A, c = 19.841(3) A, alpha = 101.91(2) degrees, beta = 97.144(8) degrees, gamma = 100.206(9) degrees, and Z = 1. In the oligomeric molecule of 1, six DMSO ligands bridge seven dirhodium tetra(trifluoroacetate) units in a bidentate fashion via S and O atoms, and two additional DMSO molecules terminate the chain. In the structure of the monoadduct Rh2(O2CCF3)4(DMSO) (2), the dirhodium blocks are bridged through the O atoms of DMSO ligands, forming a one-dimensional polymeric chain. Compound 3 also has an infinite chain structure with the molecules of dimethyl sulfoxide acting in a bidentate mu-DMSO-S,O mode. Every second DMSO molecule is missing in 3, so that two of every three Rh2(O2CCF3)4 units are associated through the O atoms of carboxylate groups to give the overall composition [Rh2(O2CCF3)4]3(DMSO)2.
The interaction between octachlorodirhenium anions and diethylphosphine has been shown to strongly depend on reaction conditions, mainly the nature of the solvent and the amount of phosphine. As a result, novel dirhenium products with oxidation states ranging from Re(II) to Re(IV) have been obtained. The reaction of [Re(2)Cl(8)](2)(-) with an excess of PEt(2)H in dichloromethane or acetonitrile led to the first example of a face-sharing complex of rhenium(IV) with three phosphido-bridges, namely [Bu(n)(4)N][Re(2)(&mgr;-PEt(2))(3)Cl(6)] (1). The unusual edge-sharing Re(2)(&mgr;-PEt(2))(2)Cl(4)(PEt(2)H)(4) (2) complex of rhenium(III) with C(i)() core symmetry, containing both terminal phosphines and phosphido-bridges, has been obtained by carrying out the reaction with an excess of PEt(2)H in a benzene (or propanol) - HCl mixture at room temperature. A new example of the 1,2,7,8-type of dirhenium(II) complex, Re(2)Cl(4)(PEt(2)H)(4) (3), having diethylphosphine ligands located cis on each Re atom, has been isolated from the reaction of [Re(2)Cl(8)](2)(-) with PEt(2)H in an ethanol-HCl medium. The solid-state structures of complexes 1-3 have been investigated by X-ray crystallography. Complexes 1 and 2 both crystallized in two forms: [Bu(n)(4)N][Re(2)(&mgr;-PEt(2))(3)Cl(6)] 1a, P2(1)/n with a = 10.482(1) Å, b = 16.512(2) Å, c = 23.986(2) Å, beta = 93.637(8) degrees, and Z = 4; [Bu(n)(4)N][Re(2)(&mgr;-PEt(2))(3)Cl(6)].1.5 C(7)H(8) 1b, C2/c with a = 38.746(9) Å, b = 10.322(2) Å, c = 27.277(3) Å, beta = 110.35(1) degrees, and Z = 8; Re(2)(&mgr;-PEt(2))(2)Cl(4)(PEt(2)H)(4) 2a, P2(1)/n with a = 11.081(3) Å, b = 11.029(3) Å, c = 15.627(2) Å, beta = 90.05(1) degrees, and Z = 2; 2b, P2(1)/c with a = 16.094(3) Å, b = 15.193(3) Å, c = 15.548(3) Å, beta = 100.98(3) degrees, and Z = 4. X-ray data for complex Re(2)Cl(4)(PEt(2)H)(4) 3 are as follows: P2(1)/n with a = 10.445(2) Å, b = 10.113(3) Å, c = 13.473(2) Å, beta = 102.17(2) degrees, and Z = 2. Three bridging &mgr;-PEt(2) groups in the face-sharing complex 1 span a short metal-metal distance of 2.4060(6) Å, averaged over 1a and 1b, with a small Re-PEt(2)-Re angle of 61.34(7) degrees. The rhenium-rhenium bond length in the edge-sharing complex 2 is 2.7545(7) Å, averaged over 2a and 2b, while the bridging Re-PEt(2)-Re angle is 72.16(6) degrees, and the P-Re-P angle for the terminal phosphine ligands is 87.11(7) degrees. The Re-Re bond distance in 3, 2.2533(8) Å, is typical for triply bonded dirhenium complexes, and the P-Re-P angle for the cis phosphine groups is 93.12(6) degrees.
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