Structural Study of Antimony Compounds by 121Sb Mossbauer Spectroscopy

在20K下测量了16个晶体结构已知的Sb(III)化合物和51个未知结构的Sb(III)化合物的穆斯堡尔谱。根据观察到的穆斯堡尔参数(特别是同分异能位移和四极耦合常数e^2gq)与Sb(III)原子周围具有立体化学活性的孤对电子(E)的组态类型之间的关系，得出了以下三个结论：1.在N，O配位化合物中，(Delta)(和e^2gq)按SbO_3E(Psi)-四面体，Sb_2O_3(接近)SbO_4e(Psi)-三角双锥，[Sb_2(Tart)_2]^&lt；2-gt；)&gt；SbO_6e(E在轴向位置；(Psi)-五方双锥，Sb(Ox)_3^&lt；3-&gt；)&gt；SbX_6e(E在赤道位置；(PSI)-五方双锥，(Hedta)2.在S配位化合物中，[Sb(SR)_3])和[Sb(SR)_3])&gt；-三角双锥，KSbS_2)&gt；Sb-S_3Short S_3long E(&lt；psi&gt；-单八面体，[Sb(S_2COR)_3]，[Sb(S_2P(OR)_2)_3])[SbS_6e(&lt；psi&gt；-五方双锥，[Sb(S_2PPh_2)_3])&gt；SbCl_6(八面体，M_3[SbCl_6])。孤字对的字符按上述顺序从左到右递增，p字符按相同顺序递减。S或氯配位的Sb(III)原子比配位的O或N原子配位的Sb(III)原子具有更小的e^2gQ，两者具有相同的构型。用穆斯堡尔谱技术成功地研究了Sb(III)络合物在冷冻溶液中的结构、Sb(III)络合物的热解和辐解以及有机Sb(V)络合物的结构和成键。

^<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.