Frederick J. Hollander

Insertion of alkynes into zirconium-nitrogen bonds leading to 2,3-diazametallacyclopentenes. Generation and reactivity of Cp2Zr(N2Ph2)

Methyl η2-1,2-diphenylhydrazido(1−)zirconocene (1) has been synthesized from the monopotassium salt of 1,2-diphenylhydrazine and Cp2Zr(Me)(Cl). Heating 1 in THF causes extrusion of methane, generating the transient hydrazido complex Cp2Zr(N2Ph2) (2) which is trapped by solvent to yield the THF adduct Cp2Zr(N2Ph2)(THF) (3). The THF ligand of compound 3 was replaced with a variety of σ-donor ligands to form the ligated hydrazido complexes Cp2Zr(N2Ph2)(L) (L  pyridine) (4), PMe3 (5), NCPh (6) and CNCMe3 (7)). Compound 4 was characterized by X-ray diffraction. The THF adduct 3 also undergoes a reaction involving insertion of alkynes into one of its metal-nitrogen bonds. Thus, reaction of 3 with 2-butyne and 3-hexyne leads to zirconocene 2,3-diazametallacyclopentenes 8 and 9 respectively. The structure of these metallacycles was supported by an X-ray diffraction study of 8. Compound 3 also reacted with phenylacetylene and acetophenone via deprotonation to furnish the η2-hydrazido(1−)acetylide (10) and enolate (11), respectively.

New mixed-metal clusters via metal hydride coupling. Synthesis and crystal structures of [(µ2-H)Os3W(CO)12(η5-C5H5)] and [(µ2-H)3Os3W(CO)11(η5-C5H5)]

The reaction of [Os3(CO)10(NCMe)2] with the hydrido-complex [HW(CO)3(η5-C5H5)] under mild conditions yields the heteronuclear metal carbonyl hydride complexes [(µ2-H)Os3W(CO)12(η5-C5H5)](1) and [(µ2-H)3Os3W(CO)11(η5-C5H5)](2); the complexes have been characterized by X-ray diffraction studies and the locations of the bridging hydride ligands have been ascertained.

Europium-doped barium bromide iodide

Single crystals of Ba0.96Eu0.04BrI (barium europium bromide iodide) were grown by the Bridgman technique. The title compound adopts the ordered PbCl2 structure [Braekken (1932 ▶). Z. Kristallogr. 83, 222–282]. All atoms occupy the fourfold special positions (4c, site symmetry m) of the space group Pnma with a statistical distribution of Ba and Eu. They lie on the mirror planes, perpendicular to the b axis at y = ±0.25. Each cation is coordinated by nine anions in a tricapped trigonal prismatic arrangement.

A crystallographic analysis of C60(Buckminsterfullerene)

Crystallographic analysis of C60 grown from a hexane solution revealed a structure which is neither hexagonal nor cubic closest packed [space group P63/m, a= 33.54(1), c= 10.113(8)A]; packing models which are consistent with the Patterson map are described.

Characterization and X-ray crystal structure of a monomeric germylene derivative, Ge(acac)I (hacac = acetylacetone)

The complex Ge(acac)I (Hacac = acetylacetone) has been characterized and its structure determined by a single-crystal X-ray structural analysis; the monomeric molecule is pyramidal with bond lengths Ge–I, 2·736(1) and Ge–O, 1·914(5) and 1·931(5)A and bond angles O–Ge–O, 91·38(22) and I–Ge–O, 91·60(16) and 93·92(16)°.

Preparation, purification, and X-ray crystal structure of a dimeric manganese(IV) porphyrin complex

The highly reactive dimeric complex µ-oxo-bis[azidotetraphenylporphyrinatomanganese(IV)] has been prepared, purified, characterized by X-ray crystallography and other physical methods, and some of its reaction examined.