Search

In this paper the reactions of iron(II) hydrides 6 – 10 formed by selective C F/C H bond activation in fluoroaryl-imines were reported. Iron hydrides 6 and 7 reacted with haloalkane to give rise to the corresponding iron halides 11 and 12 with the mer -rearrangement of the three trimethylphosphine ligands. The related trifluoromethylcarboxyl iron complexes 13 and 14 with the carboxyl group as monodentate ligand were obtained from the reactions of hydrides 8 and 9 with F 3 CCOOH. The reaction of iron hydride 6 with Lewis acid LiBF 4 delivered ionic iron complex 15 . Both the reaction of iron hydride 10 with Me 3 SiC C H and the reaction of iron bromide 11 with Me 3 SiC CLi could provide the derivative trimethylsilylacetylenyl iron(II) complexes 16 and 17 respectively. The molecular structures of complexes 12 , 13 and 17 were determined by single crystal X-ray diffraction. [ABSTRACT FROM AUTHOR]

The preligand pyridine-2-amino(methyl)-dimethylsilane ( 1 ) was used to synthesize silyl iron hydride. Iron(II) hydride FeH(N( κ N-C 5 H 4 N)Me(SiMe 2 ))(PMe 3 ) 3 ( 2 ) was obtained through the reaction of 1 and Fe(PMe 3 ) 4 via the activation of one Si H bond and the coordination of nitrogen atom of pyridine. The substitution reaction of complex 2 with haloalkane (CH 3 I and EtBr) delivered complexes FeX(N( κN -C 5 H 4 N)Me(SiMe 2 ))(PMe 3 ) 3 (X = I ( 3 ); Br ( 4 )). Complex 2 reacting with acetylacetone resulted in the formation of Fe(acac)(N( κN -C 5 H 4 N)Me(SiMe 2 ))(PMe 3 ) 3 ( 5 ). However, the insertion products Fe(η 3 -OCOH)(N( κ N-C 5 H 4 N)Me(SiMe 2 ))(PMe 3 ) 3 ( 6 ) and Fe(η 3 -Ph-NCOH)(N( κN -C 5 H 4 N)Me(SiMe 2 ))(PMe 3 ) 3 ( 7 ) were formed through the insertion of the unsaturated bonds into Fe H bond. Complex 6 could also be synthesized through the substitution reaction of 2 with HCOOH. The molecular structures of complexes 2 and 4 – 7 were determined by single crystal X-ray diffraction. [ABSTRACT FROM AUTHOR]

A series of reactions of different silver thiolates, AgSR (R = Mes (mesityl), Nph (naphthyl), Cy (cyclohexyl)), with bidentate phosphanes was performed yielding a bunch of new compounds, which were characterized by single crystal X-ray diffraction. Depending on the nature of the thiolate and the phosphane the solid state structure of the products varies from discrete complexes or clusters to a 3-dimensional coordination network. The mesityl group favors the formation of trinuclear units which are then linked in one, e.g. [Ag3(SMes)3(dpph)2] (5), two, e. g. [Ag3(SMes)3 (dpppt)2] (4), or three dimensions [Ag3(SMes)3(dppb)2] (3), via the phosphanes. With naphthyl and cyclohexyl groups mostly clusters are formed which are either isolated with some phosphanes in their ligand sphere, e.g. [Ag12(SCy)12(dpppt)2] (13), or additionally linked by the phosphanes to form 1-dimensional chains, e.g. [Ag12(SCy)12(dppo)] (17). [ABSTRACT FROM AUTHOR]

Abstract: Interaction of Ag(CF3CO2) with bis(diphenylphosphino)amide (dppa) in THF gave a tetranuclear Ag4-coplanar silver(I) complex [Ag4(μ-dppa)2(μ4-O2PPh2)2(μ-CF3CO2)2] (1). The trinuclear trigonal-bipyramid copper(I) complex [Cu3(μ3-Cl)2(μ-dppa)3][CuCl2] (2) was obtained from the reaction of [CuCl] powder with bis(diphenylphosphino)amide (dppa) in THF. Treatment of 2 with (Me3Si)2Se in THF afforded a μ8-selenide-centered octanuclear copper(I) complex [Cu8(μ8-Se)(μ4-Se)(μ4-SeH)3(μ-dppa)4][(Ph2PO)2N] (3). The structures of 1–3 were determined by single-crystal X-ray diffraction analyses. Complex 1 comprises a rectangular Ag4 array with each edge bridged with a pair of μ-dppa, μ4-O2PPh2 and μ-CF3CO2 ligands that are approximately perpendicular to each other. Complex 2 contains a trigonal-bipyramid [Cu3(μ3-Cl)2]+ core surrounded by three μ-dppa ligands. The cationic complex in 3 consists of four [Cu2(μ-dppa)] fragments side-capped by one μ4-Se and three μ4-SeH ligands and center-connected by a μ8-Se atom. [Copyright &y& Elsevier]

From solutions of seleno bridged triangular cluster Mo3Se4(aq)4+ in HCl, crystalline adducts with cucurbituril (Cuc, C36H36N24O12) of different composition, depending on HCl concentration, were isolated. From 2 M HCl, a monosubstituted cationic cluster crystallizes as {[Mo3Se4Cl(H2O)8]2(C36H36N24O12)}Cl6·16H2O (1). Increase in HCl concentration to 6 M gives a pentasubstituted anionic species, (H3O)2[Mo3Se4Cl5(H2O)4]2(C36H36N24O12)·15H2O (2). The crystal structures of 1 and 2 were determined by X-ray crystallography. Each portal of Cuc in 1 is covered with cluster cations [Mo3Se4Cl(H2O)8]3+ like a ‘lid’ on a ‘barrel’. Six water molecules in the trans position to the core μ2-Se form complementary hydrogen bonds with oxygen atoms of Cuc (O⋯O, 2.713–3.067 A˚). In 2 the complementarity is lost and the main structure building factor is short Se⋯Se interactions (Se⋯Se, 2.96–3.43 A˚) between two adjacent anionic clusters. Stereochemistry of halide substitution in the triangular clusters M3Q4 is analyzed. [Copyright &y& Elsevier]