Leonidas J. Jones

Isolation and X-Ray Crystal Structures of Li?mu 2-As(SiMe3)2MU 3-As(SiMe3)2(THF)2 and (Me3Si)2AsLiTHF)22.

Abstract The lithium arsenides {Li2[μ2-As(SiMe3)2] [μ3-As(SiMe3)2](THF)}2 (I) (THF = tetrahydrofuran) and [(Me3Si)2AsLi(THF)2]2 (II) were isolated and their solid-state structures determined by X-ray methods. Compound I crystallizes in the monoclinic system, space group P21/c, with a = 10.147(1)A, b = 19.665(2)A, c = 16.768(2)A, β = 107.78(1)° and Z = 2. The core structure consists of an [LiAs]4 ladder-like framework with four antiparallel adjacent As-Li rungs. The two lithium atoms of the central ring each bridge three arsenic centers while the two lithium atoms belonging solely to the outer rings each span two arsenic atoms and are coordinated to one THF molecule. Monoclinic crystals of compound II belong to space group C2/c, with a = 17.877(4) A, b = 14.077(3) A, c = 19.006(4) A, β = 109.16(2)° and Z = 4. The structure consists of a centrosymmetric dimer containing a four-membered As-Li-As-Li ring wherein each lithium atom is coordinated to two molecules of THF.

Dehalosilylation reactions involving E(sime3)3 and Ph2Incl. Synthesis and X-ray structures of [Ph2Ine(SiMe3)2]2 (E = P or As)

Abstract Combining P(SiMe3)3 or As(SiMe3)3 with Ph2InCl in a 1:1 mole ratio results in the elimination of Me3SiCl via a dehalosilylation reaction to yield [Ph2InP(SiMe3)2]2 (I) and [Ph2InAs(SiMe3)2]2 (II), respectively. X-ray structures were determined for I and II. The (InP)2 core of dimer I is planar, whereas in dimer II the (InAs)2 ring is slightly puckered.

Synthesis and molecular structures of R(Me3CCH2)2In.E(SiMe3)3 (R=Me3CCH2, E=P or As ; R=Me, E=P)

Abstract Combining P(SiMe 3 ) 3 or As(SiMe 3 ) 3 with (Me 3 CCH 2 ) 3 In in a 1:1 mole ratio yields simple adducts (Me 3 CCH 2 ) 3 In·P(SiMe 3 ) 3 ( I ) and (Me 3 CCH 2 ) 3 In·As(SiMe 3 ) 3 ( II ), respectively. Addition of (Me 3 CCH 2 ) 2 InCl to a diethyl ether solution of LiP(SiMe 3 ) 2 produces Me(Me 3 CCH 2 ) 2 In·P(SiMe 3 ) 3 ( III ). X-ray crystal structures have been determined for compounds ( I ), ( II ) and ( III ).

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

On the Synthesis of Mixed-Metal and Mixed-Pnicogen 13-15 Ring Systems

Abstract : Several pathways toward the synthesis of mixed-metal and mixed-pnicogen 13-15 ring systems have been explored. Equilibration reactions have proven successful toward the preparation of the latter compounds while most attempts to prepare mixed-metal compounds have resulted in unexpected and novel 13-15 species. These reactions and their products are discussed.