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Structural Study of Antimony Compounds by 121Sb Mossbauer Spectroscopy

121Sb 穆斯堡尔谱研究锑化合物的结构

基本信息

批准号：
60470049
负责人：
TAKEDA Masuo
金额：
$ 3.78万
依托单位：
Toho University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1985
资助国家：
日本
起止时间：
1985 至 1987
项目状态：
已结题

项目摘要

^<121> Sb mossbauer spectra of 16 antimony(III) compounds of accurately known crystal structure and 51 other such compounds of unknown structure have been measured at 20 K. The following three conclusions were drawn from the observed relationship between the mossbauer parameters (especially isomer shift, <delta> and quadrupole coupling constant, e^2gQ) and the type of configuration around the Sb(III) atoms with stereochemically active lone pair electrons(E).1. In N-, O-coordinated compounds, (delta) (as well as e^2gQ) decreases in the order SbO_3E (psi.)-tetrahedral, Sb_2O_3 (approaches) SbO_4E (psi)-trigonal bipyramidal, [Sb_2(tart)_2]^<2->) > SbO_6E (E at axial position; (psi)-pentagonal bipyramidal, Sb(ox)_3^<3->) > SbX_6E (E at equatorial position; (psi)-pentagonal bipyramidal,(Hedta).2. In S-, C1-coordinated compounds, <delta> (as well as e^2gQ) decreases in the order SBS_3E<psi>-tetrahedral, [Sb(SR)_3]) > SbS_4E <psi>-trigonal bipyramidal, KSbS_2) > Sb- S_3shortS_3longE (<psi>-monocapped octahedral, [Sb(S_2COR)_3], [Sb(S_2P(OR)_2)_3]) [ SbS_6E (<psi>- pentagonal bipyramidal, [Sb(S_2PPh_2)_3]) > SbCl_6 (octahedral, M_3[SbCl_6]). The character of the lone pair is considered to increase in the above order from left to right, the p-character decreasing in the same order.3. The Sb(III) atoms coordinated by S or Cl atoms have smaller e^2gQ than those coordinated by O or N atoms, both of which have identical configurations.In addition. ^<121>Sb Mossbauer technique was successfully applied to the studies on sturcture of the antimony(III) complexes in the frozen solution, pyrolysis as well as radiolysis of antimony(III) complexes, and structure and bonding of the organic antimony(V) complexes.

在<121>20 K下测量了16种已知晶体结构的锑（Ⅲ）化合物和51种未知结构的锑（Ⅲ）化合物的穆斯堡尔谱。从观察到的穆斯堡尔参数（特别是同分异构体位移和<delta>四极耦合常数e^2gQ）与Sb（III）原子周围具有立体化学活性孤对电子（E）的构型类型之间的关系得出以下三个结论。在N-，O-配位化合物中，（δ）（以及e^2gQ）以SbO_3E（psi.）SbO_4 E（psi）-三角双锥，[Sb_2（tart）_2]^<2->）> SbO_6 E（E轴向位置;（psi）-五角双锥，Sb（ox）_3^<3->）> SbX_6 E（E赤道位置;（psi）-五角双锥，（Hedta）。在S-、C1-配位化合物中，<delta>（以及e^2gQ）按以下顺序减小：SBS_3E<psi>-四面体，[Sb（SR）_3]）> SbS_4E<psi>-三角双锥，KSbS_2）> Sb-S_3shortS_3longE（<psi>-单帽八面体，[Sb（S_2COR）_3]，[Sb（S_2P（OR）_2）_3]）[ SbS_6E（<psi>-五角双锥，[Sb（S_2PPh_2）_3]）> SbCl_6（八面体，M_3[SbCl_6]）.孤对电子的特性被认为是从左到右按上述顺序增加，p-特性按相同顺序减少。Sb（III）原子与S或Cl原子配位时的e^2gQ值小于与O或N原子配位时的e^2gQ值，而O或N原子的构型相同。用<121>穆斯堡尔谱研究了锑（Ⅲ）配合物在冷冻溶液中的结构，锑（Ⅲ）配合物的热分解和辐解，以及有机锑（Ⅴ）配合物的结构和成键。