C.D. Bryan

Preparation and Solid State Characterization of 4,4'-Bis(1,2,3,5-dithiadiazolyl)

The reaction of oxamidrazone with sulfur dichloride affords 4,4′-bis(1,2,3,5-dithiadiazolium) dichloride, which can be reduced with triphenylantimony to the corresponding bis(1,2,3,5-dithiadiazolyl) diradical; the solid state structure and transport properties of the dimer [S2N2CCN2S2]2are reported.

Reaction of CpRu(PPh3)2Cl with six-member cyclothioethers. Structures of the [CpRu(PPh3) x L]Y complexes (L = pentamethylene sulfide, x = 2, Y = BF4−; L = 1,3-dithiane; 1,3,5-trithiane, x = 2, Y = CF3SO3−; L = 1,4-dithiane, x = 1, Y = BF4−)

The synthesis of a series of ruthenium complexes with cyclothioether ligands is reported. The compounds were characterized by X-ray diffraction techniques. The molecular structures of [CpRu(PPh3)2(pms)]BF4 (1), [CpRu(PPh3)2(1,3-dithiane)]OTfl (2), [CpRu(PPh3)2(1,3,5-trithiane)]OTfl (3), and [CpRu(PPh3)(1,4-dithiane)]BF4 (4) show chelation occurs only when the sulfur atoms are separated by at least two C atoms, creating a ligand bite size large enough to chelate. Cell parameters: 1, space group P21/c, a = 14.601(4), b = 19.102(10), c = 14.751(7) Å, β = 98.28(3)○; 2, space group P21/c, a = 12.859(7), b = 15.576(3), c = 22.126(11) Å, β = 102.22(4)○; 3, space group P21/c, a = 12.7320(20), b = 15.571(5), c = 22.287(4) Å, β = 101.812(14)○; 4, space group Pbca, a = 11.2010(10), b = 16.321(7), c = 28.966(4) Å. Compounds 2 and 3 are X-ray isomorphous. The Ru–S bond lengths range from 2.341(3), 2.365(3) Å in compound 4 to 2.382(4) Å in compound 2. Upon chelation (compound 4), with subsequent loss of PPh3, the Ru–P bond shortens to 2.327(3) Å. This may be due to reduced steric hindrance about the Ru atom. No evidence for C–S bond lengthening is observed.

HETEROBIMETALLIC (PD,PT,CU) COMPLEXES OF HEXAPYRAZOLYLCYCLOTRIPHOSPHAZENE VIA SIMULTANEOUS GEMINAL (N2) AND NONGEMINAL (N3) COORDINATION MODES

Abstract Synthesis and spectroscopy of four heterobimetallic compounds containing the metal centres Cu(II)-Pd(II) and Cu(II)-Pt(II) with the multidentate nitrogen donor ligand hexakis (3,5-dimethyl-pyrazolyl)cyclotriphosphazene, (HPCTP) are reported. The complexes HPCTP·CuCl2·MX2 (M = Pd, X = Cl (3) or Br (4) and M = Pt, X = Cl (5) or Br (6)) were obtained by treating the metal-containing ligands HPCTP°CuX2 X = Cl(l) or Br(2)) with M(PhCN)2Cl2(M = Pd or Pt). The electronic absorption spectra and electron paramagnetic resonance data indicate the copper in these compounds has a distorted trigonal bipyramidal geometry. A single crystal X-ray determination of 4 is reported. The crystals of 4 are monoclinic with a = 10.570(2), b = 28.863(4), c = 16.009(1)A, β = 98.71(2)°, V = 4827(1)A3, Z = 4, D c = 1.65 g cm−3 and space group P21/c. The geometry about copper is trigonal bipyramidal with mean distances of Cu-N(pz) = 1.987(13), Cu-N(ctp) = 2.352(11) and Cu-Cl = 2.315(10)A while that of palladium is square plana...

Structure of chlorohydroxonitrosyl(terpyridine)ruthenium(II) hexafluorophosphate

The title complex has the NO grouptrans to the hydroxyl ligand and the chloride ion in the plane of the tripyridyl ligand. The Ru−O and Ru−N(O) distances are 1.939(5) Å and 1.764(6) Å, respectively; the Ru−N−O bond angle is 171.7(6)0. These values are consistent with previously reported shortening of Ru−O distances whentrans to a linear NO ligand. The space group of the structure isP21/c, witha=9.7213(9) Å,b=13.9318(11) Å,c=14.523(4) Å, and β=105.820(13)0.

Preparation, Structure and Chemistry of a Novel, Disjoint Diradical, 4,4′-Bis(1,2,3,5-Dithiadiazolyl)

Abstract The reaction of oxamidrazone with SCl2 affords 4,4′-bis(1,2,3,5-dithiadiazolium) dichloride, which can be reduced to the corresponding bis(1,2,3,5-dithiadiazolyl) diradical; the electronic structure of the diradical is discussed, and the solid state structure, charge transfer chemistry and transport properties of the dimer [S2N2CCN2S2]2 are described.

Recent Results in the Preparation of Molecular Conductors Based on P-Type Doped π-Radicals

Abstract The p-type doping of neutral polyfunctional π-radicals with iodine has revealed interesting electronic and structural features. Alternative preparative routes such as electrocrystallization have allowed the isolation of compounds not normally obtainable via sublimation methods.