Optically Active Vanadium(IV) and (V) Complexes Containing (<i>S</i>)-<i>N</i>-[1-(2-Pyridyl)ethyl]iminodiacetate Ion
作者:Kenichi Okazaki、Kazuo Saito
DOI:10.1246/bcsj.55.785
日期:1982.3
New optically active vanadium(IV) and (V) and mixed valence(IV,V) complexes containing a quadridentate ligand (S)-N-[1-(2-pyridyl)ethyl]iminodiacetate (S-peida2−) have been prepared: i.e. uninuclear distorted octahedral [VIVO(S-peida)(H2O)] and Li[Vv(O)2(S-peida)], a mixed valence binuclear Na[V2IV,VO3(S-peida)2], and an oxo-peroxo complex Na[VvO(O2(2−))(S-peida)]. The tertiary amino nitrogen of S-peida2− occupies the trans position to the oxo ligand in the first three complexes, but trans to the peroxo ligand in the last complex. Three absorption bands of [VIVO(S-peida)(H2O)] in the region from 10000 to 30000 cm−1 have been assigned to the d-d transitions, dxy→(dxz,dyz), dxy→dz2−y2, and dxy→dz2, in the order of increasing frequency. The mixed valence complex gives an intervalence transfer band and two d-d bands in the region from 9000 to 25000 cm−1. It gives a negative and a positive CD peak corresponding to the intervalence transition. The VV(O)2 and the VVO(O2) complex give a characteristic absorption shoulder at 25000 and a peak at 23500 cm−1 with corresponding weak negative CD peaks, respectively. They are assigned to charge transfer bands from oxo and peroxo to VV, respectively. The sign of CD peaks seems to be governed mostly by asymmetric arrangement of the ligating atoms and asymmetric deviation of ligating atoms from regular octahedron.
即无核畸变八面体[VIVO(S-peida)(H2O)]和 Li[Vv(O)2(S-peida)]、混合价双核 Na[V2IV,VO3(S-peida)2]以及氧化过氧配合物 Na[VvO(O2(2-))(S-peida)]。在前三个络合物中,S-peida2- 的三级氨基氮与氧配体的位置呈反式,而在最后一个络合物中,与过氧配体的位置呈反式。[VIVO(S-peida)(H2O)]在 10000 至 30000 cm-1 区域的三条吸收带按频率递增的顺序分别归属于 d-d 转变,即 dxy→(dxz,dyz), dxy→dz2-y2 和 dxy→dz2。混价复合物在 9000 至 25000 cm-1 区域给出了一个间隔转移带和两个 d-d 带。它给出了一个负的和一个正的 CD 峰,与间隙转变相对应。VV(O)2 和 VVO(O2) 复合物分别在 25000 和 23500 cm-1 处给出了一个特征吸收肩带和一个峰值,以及相应的弱负 CD 峰。它们分别属于从氧和过氧到 VV 的电荷转移带。CD 峰的符号似乎主要受配位原子的不对称排列和配位原子与规则八面体的不对称偏差的影响。