Arsenic(III) halide complexes with acyclic and macrocyclic thio- and selenoether coligands: synthesis and structural properties.
Arsenic(III) halide complexes with acyclic and macrocyclic thio- and selenoether coligands: synthesis and structural properties.
复制标题
砷（III）卤化物与无环和大环硫代和硒醚共配体的配合物：合成和结构特性。
作者：
N. Hill;W. Levason;G. Reid
合成了新的配合物[AsBr（3）[MeS（CH（2））（2）SMe]]，[AsX（3）]（[9]aneS（3））]（X = Cl、Br或I;[9]aneS（3）= 1，4，7-三硫杂环壬烷），[AsCl（3）（[14]aneS（4））]（[14]aneS（4）= 1，4，8，11-四硫杂环十四烷），[AsX（3）（[8]aneSe（2））]（[8]aneSe（2）= 1，5-二硒环辛烷），[（AsX（3））（2）（[16]aneSe（4））]（[16]aneSe（4）= 1，5，9，13-四硒环十六烷）和[（AsBr（3））（2）（[24]aneSe（6））]（[24] aneSe（6）= 1，5，9，13，17，21-六硒环二十四烷）。它们是由适当的AsX（3）和1摩尔当量的硫醚或硒醚配体在无水CH（2）Cl（2）（或对于X = I为THF）溶液中直接反应得到的。用微量分析、IR和1HNMR对产物进行了表征。在溶液中，它们广泛地离解，反映了AsX（3）的弱刘易斯酸性。AsX（3）与MeSe（CH（2））（2）SeMe或MeC（CH（2）EMe）（3）（E = S或Se）反应仅得到油状物。用Me（2）S、MeE（CH（2））（2）EMe或[9]aneS（3）处理PCl（3）或PBr（3）不能得到固体络合物，并且从NMR光谱中没有证据表明溶液中形成任何加合物。描述了As（III）的第一系列硫醚和硒醚络合物的晶体结构：[AsBr（3）[MeS（CH（2））（2）SMe]]，C（4）H（10）AsBr（3）S（2），a = 10.2818（6）A，B = 7.8014（5）A，c = 14.503（1）A，β = 102.9330（2）度，单斜晶系，P2（1）/c，Z = 4;[AsI（3）[MeS（CH（2））（2）SMe]]，C（4）H（10）AsI（3）S（2），a = 9.1528（1）A，B = 11.5622（2）A，c = 12.0939（2）A，β = 93.863（1）度，单斜晶系，P2（1）/n，Z = 4;[AsCl（3）]（[9]aneS（3））]，C（6）H（12）AsCl（3）S（3），a = 17.520（4）A，B = 17.520（4）A，c = 16.790（7）A，四面体，I4（1）cd，Z = 16;[AsCl（3）]（[14]aneS（4））]，C（10）H（20）AsCl（3）S（4），a = 13.5942（2）A，B = 7.7007（1）A，c = 18.1270（3）A，β = 111.1662（5）度，单斜晶系，P2（1）n，Z = 4;[（AsCl（3））（2）（[16]aneSe（4））]，C（12）H（24）As（2）Cl（6）Se（4），a = 9.764（3）A，B = 13.164（1）A，c = 10.627（2）A，β = 114.90（1）度，单斜晶系，P2（1）（）/n，Z = 2;[（AsBr（3））（2）（[16]aneSe（4））]，C（12）H（24）As（2）Br（6）Se（4），a = 10.1220（1）A，B = 13.4494（2）A，c = 10.5125（2）A，β = 113.49（2）度，单斜晶系，P2（1）（）/n，Z = 2。[AsBr（3）[MeS（CH（2））（2）SMe]]和[AsI（3）[MeS（CH（2））（2）SMe]]显示了离散的μ（2）-卤代As（2）X（6）二聚体结构，其中包含畸变的八面体As（III），与二硫醚配体螯合。[AsCl（3）（[9]aneS（3））]采用离散的分子畸变八面体几何构型，硫醚表现为弱配位的面封端配体。[AsCl（3）（[14]aneS（4））]形成一个无限的片层，在每个As上有两个μ（2）-氯配体，但桥连到两个不同的As中心。每个大环通过一个S原子与两个相邻的As中心配位，得到一个顺式八面体Cl（4）S（2）供体组As（III）。[（AsCl（3））（2）（[16]aneSe（4））]和[（AsBr（3））（2）（[16]aneSe（4））]的结构均为二维片状结构，其中μ（2）-二卤代As（2）X（6）二聚体通过μ（4）-四硒醚大环交联，在每个As中心形成一个无序的cis-X（4）Se（2）供体组.这些物种进行了比较，其锑（III）和铋（III）的类似物在适当的情况下。
The preparations of the new complexes [AsBr(3)[MeS(CH(2))(2)SMe]], [AsX(3)([9]aneS(3))] (X = Cl, Br or I; [9]aneS(3) = 1,4,7-trithiacyclononane), [AsCl(3)([14]aneS(4))] ([14]aneS(4) = 1,4,8,11-tetrathiacyclotetradecane), [AsX(3)([8]aneSe(2))] ([8]aneSe(2) = 1,5-diselenacyclooctane), [(AsX(3))(2)([16]aneSe(4))] ([16]aneSe(4) = 1,5,9,13-tetraselenacyclohexadecane), and [(AsBr(3))(2)([24]aneSe(6))] ([24]aneSe(6) = 1,5,9,13,17,21-hexaselenacyclotetracosane) are described. These are obtained from direct reaction of the appropriate AsX(3) and 1 mol equiv of the thio- or selenoether ligand in anhydrous CH(2)Cl(2) (or thf for X = I) solution. The products have been characterized by microanalysis and IR and (1)H NMR spectroscopy. In solution they are extensively dissociated, reflecting the weak Lewis acidity of AsX(3). Reaction of AsX(3) with MeSe(CH(2))(2)SeMe or MeC(CH(2)EMe)(3) (E = S or Se) gave only oils. Treatment of PCl(3) or PBr(3) with Me(2)S, MeE(CH(2))(2)EMe, or [9]aneS(3) failed to give solid complexes, and there was no evidence from NMR spectroscopy for any adduct formation in solution. The crystal structures of the first series of thioether and selenoether complexes of As(III) are described: [AsBr(3)[MeS(CH(2))(2)SMe]], C(4)H(10)AsBr(3)S(2), a = 10.2818(6) A, b = 7.8014(5) A, c = 14.503(1) A, beta = 102.9330(2) degrees, monoclinic, P2(1)/c, Z = 4; [AsI(3)[MeS(CH(2))(2)SMe]], C(4)H(10)AsI(3)S(2), a = 9.1528(1) A, b = 11.5622(2) A, c = 12.0939(2) A, beta = 93.863(1) degrees, monoclinic, P2(1)()/n, Z = 4; [AsCl(3)([9]aneS(3))], C(6)H(12)AsCl(3)S(3), a = 17.520(4) A, b = 17.520(4) A, c = 16.790(7) A, tetragonal, I4(1)cd, Z = 16; [AsCl(3)([14]aneS(4))], C(10)H(20)AsCl(3)S(4), a = 13.5942(2) A, b = 7.7007(1) A, c = 18.1270(3) A, beta = 111.1662(5) degrees, monoclinic, P2(1)()/n, Z = 4; [(AsCl(3))(2)([16]aneSe(4))], C(12)H(24)As(2)Cl(6)Se(4), a = 9.764(3) A, b = 13.164(1) A, c = 10.627(2) A, beta = 114.90(1) degrees, monoclinic, P2(1)()/n, Z = 2; [(AsBr(3))(2)([16]aneSe(4))], C(12)H(24)As(2)Br(6)Se(4), a = 10.1220(1) A, b = 13.4494(2) A, c = 10.5125(2) A, beta = 113.49(2) degrees, monoclinic, P2(1)()/n, Z = 2. [AsBr(3)[MeS(CH(2))(2)SMe]] and [AsI(3)[MeS(CH(2))(2)SMe]] reveal discrete mu(2)-halo As(2)X(6) dimeric structures involving distorted octahedral As(III), with the dithioether ligand chelating. [AsCl(3)([9]aneS(3))] adopts a discrete molecular distorted octahedral geometry with the thioether behaving as a weakly coordinated fac-capping ligand. [AsCl(3)([14]aneS(4))] forms an infinite sheet involving two mu(2)-chloro ligands on each As but bridging to two distinct As centers. Each macrocycle coordinates to two adjacent As centers via one S atom, giving a cis-octahedral Cl(4)S(2) donor set at As(III). The structures of [(AsCl(3))(2)([16]aneSe(4))] and [(AsBr(3))(2)([16]aneSe(4))] adopt 2-dimensional sheet structures with mu(2)-dihalo As(2)X(6) dimers cross-linked by mu(4)-tetraselenoether macrocycles, giving a disorted cis-X(4)Se(2) donor set at each As center. These species are compared with their antimony(III) and bismuth(III) analogues where appropriate.