Robert R. Whittle

Dirhenium complexes containing linked diphenylacetylene molecules from the photoreaction of H3Re3(CO)12 with PhCCPh. Crystal and molecular structures of Re2CO)5(C4Ph4)(C4Ph4) and Re2(CO)4(C6Ph6)(C2Ph2·12 hexane

Photolysis of H3Re3(CO)12 in presence of diphenylacetylene (DPA) yields Re2(CO)10, HRe(CO)5, and the three alkyne complexes Re2(CO)7(DPA)2, Re2(CO)5(C4Ph4)(DPA) (4) and Re2(CO)4(C6Ph6)(DPA) (3), the latter two which were shown by X-ray crystallography to possess linked DPA ligands. The complex Re2(CO)5(C4Ph4)(DPA) crystallizes in the triclinic space group P1 (No. 2) with a 11.277(3), b 12.301(3), c 14.851(3) A, α 97.37(2), β 104.68(2), γ 104.49(2)°, V 1889(2) A3, and Z = 2. The structure was refined using the 4548 reflections with I ⩾ 2σ(I) to give final residuals of R = 0.031 and Rw = 0.041. Complex 4 possesses a rhenacyclopentadiene group bonded to the second rhenium atom and an η2-DPA ligand bound to the rhenium atom of the metallacycle. The complex Re2(CO)4(C6Ph6)(DPA) crystallizes in the monoclinic space group P21/c (No. 14) with a 17.048(4), b 16.676(2), c 18.569(4) A, β 106.70(2)°, V 5056(3) A3, and Z = 4. For the 3568 reflections with I ⩾ 2σ(I), the structure refined to R = 0.078 and Rw = 0.074. Three of the DPA molecules in Re2(CO)4(C6Ph6)(DPA) are linked together to form a “fly-over bridge” between the two rhenium atoms. The fourth DPA molecule is η2-bound to one rhenium center.

The synthesis and structure of triphenylsiloxycyclotriphosphazenes

The triphenylsiloxy-substituted cyclotriphosphazenes, N3P3Cl5OSiPh3, gem-N3P3Cl4(OSiPh3)2, N3P3(OSiPh3)6, and N3P3(OPh)5OSiPh3, have been prepared. The synthesis of gem-N3P3Cl4(OSiPh3)2 involves the reaction of (NPCl2)3 with Ph3SiONa to form the intermediates gem-N3P3Cl4(OSiPh3)2(ONa) and gem-N3P3Cl4(ONa)2, which yield gem-N3P3Cl4(OSiPh3)2 when treated with Ph3SiCl. The compounds N3P3Cl5OSiPh3 and N3P3(OSiPh3)0 are formed by the condensation reactions of N3P3Cl5OBun and N3P3(OBun)6, respectively, with Ph3SiCl. The compound N3P3(OPh)5OSiPh3 is synthesized by the reaction between N3P3(OPh)5Cl and Et3SiONa to first give the intermediate N3P3(OPh)5ONa, which yields N3P3(OPh)5OSiPh3 when reacted with Ph3SiCl. The structural characterization and properties of these compounds are discussed. The crystal and molecular structure of gem-N3P3Cl4(OSiPh3)2 has been investigated by single-crystal X-ray diffraction techniques. The crystals are monoclinic with the space group P21/c with a = 16.850(8), b = 12.829(4), c = 18.505(15) A, and β = 101.00(6)° with V = 3927 A3 and Z = 4.

Synthesis, structure, and chemistry of a 1-thia-4-azanaphthalene

Abstract From a crystal structure determination and thermal rearrangement studies, it is evident that 1-methyl-2-carbethoxy-3-phenyl-1-thia-4-azanaphthalene is an alias for a molecule more properly represented by a name emphasizing its zwitterionic character.

Nearly regular tetrahedral geometry in a gold(I)-phosphine complex. X-Ray crystal structure of tetrakis(methyldiphenylphosphine)gold(I) hexafluorophosphate

An X-ray crystal structure determination shows the gold(I) complex with four methyldiphenylphosphine ligands to have symmetry with all Au–P bond lengths equal and nearly tetrahedral angles; further, 31P n.m.r. spectroscopy at –80 °C indicates that the nearly tetrahedral species persists in solution.

Iron-bound cyclotriphosphazenes derived from phosphazene anions. X-Ray crystal structure of N3P3Cl4(CH3)[Fe(CO)2(C5H5)]

Iron-bound cylotriphosphazene complexes have been prepared via the reactions of lithium 1-methyl-3,3,5,5-tetrachlorocyclotriphosphazenide and lithium 1-phenyl-1-triethylborata-3,3,5,5-tetrachlorocyclotriphosphazene with dicarbonylcyclopentadienyliodoiron, and their structures determined by spectroscopic and crystallographic techniques.

Ferrocene-bound cyclophosphazenes. X-Ray crystal structure of N3P3F5(C5H4FeC5H5)

Ferrocenylphosphazenes have been prepared by the reactions of lithioferrocene with hexafluorocyclo-triphosphazene or octafluorocyclotetraphosphazene, and their structures were determined by spectroscopic and crystallographic techniques.

Synthesis of a di-iron-spirocyclotriphosphazene and a tri-iron-cluster-cyclotriphosphazene

Di-iron and tri-iron-cyclophosphazene complexes have been obtained via the reactions of hexachlorocyclotriphosphazene with disodium octacarbonyldiferrates(–1), and their structures determined by spectroscopic and crystallographic techniques.