Ryan A. Baldwin

Synthesis and Characterization of a Neutral Six-coordinate Tris-adduct of an Indium(III) Trihalide. X-ray Crystal Structure of InCl3(THF)3

Abstract The reaction of InCl 3 with excess THF afforded the adduct InCl 3 (THF) 3 in a good yield (77.1% based on InCl 3 ), and the X-ray crystal structure shows it to be a hexa-coordinated tris-adduct of indium(III) chloride. The crystal structure consists of discrete monomeric units with no abnormally short intermolecular separations. The geometry about the indium atom approximates to octahedral with the three chlorine atoms (mean InCl = 2.422 A) and the oxygen atoms of each THF molecule (mean InO = 2.254 A) residing in the meridional conformation. IR spectroscopic measurements gave absorption bands near 1027 and 857 cm −1 , which are consistent with coordinated THF molecules. Variable temperature NMR studies showed that the tris-adduct was stable to disproportionation in solution between 20 and 60°C.

Synthesis and Characterization of an Organothallium-Phosphorus Adduct: Crystal Structure of (Me3SiCH2)3Tl·P(SiMe3)3

The organothallium phosphorus adduct (Me3 SiCH2)3Tl · P(SiMe3)3 (1) was prepared by combining (Me3SiCH2)3Tl and P(SiMe3)3 at room temperature. Compound 1 was characterized by 1H, 13C{1H}, and 31P{1H} NMR, partial elemental analysis, EI mass spectrometry, and single-crystal X-ray analysis, the first to be reported for a thallium-group 15 adduct. Crystal data for 1: trigonal system, space group P 31, with a = 16.063(6) A, c = 12.148(3) A, Dcalcd = 1.315 g cm−3, and V = 2714.3(11) A3 for Z = 3. Refinement converged at R = 0.042 (Rw = 0.045). The Tl-P bond length in 1, previously unreported for compounds of this type, was found to be 1.922(3) A.

Preparation and characterization of arsine derivatives: X‐ray crystal structures of As (SitBuMe2)3, As (SiMe3)2(SiPh3), Et3Ga · As(SiMe3)2(SiPh3), and As(SePh)3

Abstract : For the last decade, our laboratory has had great interest in the chemistry of silylarsines 1. These compounds, in combination with Group 13 alkyl or halogen derivatives, have been shown to be excellent starting reagents for preparing compounds which contain the Group 13 element-arsenic bond. Although the reactivity of silylarsines is well documented (vide supra), structural characterization data for these species has been limited to solution- and gas-phase measurements 2 due to their non-crystallinity. As a result, unambiguous structural information for these compounds is scant and appears to be limited to lithium-arsenide salts coordinated to donor solvents 3. Therefore, we became interested in preparing organosilylarsines which could find utility in our ongoing investigations of Group 13 element-arsenic compounds and be characterized in the solid-state. In addition to this chemistry, we wished to study systems which focused on the reactions of organosilylarsines with Group 13 and Group 16 derivatives. Through our efforts, we have been able to observe some interesting chemical phenomena and isolate several new compounds (this work). p4

X-RAY CRYSTAL STRUCTURE OF A MONOMERIC TRIS(ARSINO)GALLANE, [(Me3Si)2As]3Ga

Abstract The solid-state structure of [(Me3Si)2As]3Ga (1) has been established by single-crystal X-ray analysis. Triclinic crystals of 1 belong to the space group P1, with a = 10.7529(23), b = 10.7899(23), c = 17.55(6) A, α = 88.077(23)°, β = 84.537(23)°, γ = 60.282(16)° for Z = 2. Refinement of atomic parameters converged at R = 0.058 (Rw = 0.064) for 2378 observed reflections with I>2.5σ(I). The monomeric molecule adopts a trigonal planar configuration with Ga-As = 2.4171(23), 2.4250(22) and 2.4213(24) A, and As-Ga-As (av.) = 120.00(1)°. Compound 1 is only the second example of a monomeric tris(arsino)gallane to be structurally characterized in this manner.

Facile preparation of nanocrystalline gallium antimonide

Abstract The 1:1 reaction of GaCl3 with Sb(SiMe 3 ) 3 in pentane solution affords an intermediate material which, upon thermolysis, yields nanocrystalline GaSb with an approximate average particle size of 12 nm. The product was characterized through powder X-ray diffraction, elemental analysis, and HRTEM.