Solvent dependent crystallization of a few Hg(II) thiocarboxylates
- 作者：Suryabhan Singh ; Jyotsna Chaturvedi ; Subrato Bhattacharya<sup> ; sup><sup>bhatt99@yahoo.comsup><sup> ; sup><sup>s_bhatt@bhu.ac.insup>
- 关键词：Mercury ; Thiocarboxylate ; Triphenylphosphine ; Polytopal isomerism ; DFT
- 刊名：Inorganica Chimica Acta
- 出版年：2012
- 期刊代码：40_00201693
- 类别：ch
- 出版时间：30 April, 2012
- 卷：385
- 期：Complete
- 页码：112-118
- 文件大小：1014 K
摘要
During the process of crystallization of newly synthesized heterobimetallic complexes [(Ph<sub>3sub>P)<sub>2sub>Cu(渭-SCOR)<sub>2sub>Hg(SCOR)] [R = Ph (<strong class="boldFont">1strong>), th (thiophene) (<strong class="boldFont">2strong>)] Hg(II) thiocarboxylate complexes were isolated. In chloroform/diethyl ether a phosphine migration led to the formation of Hg(Ph<sub>3sub>P)(SCOPh)<sub>2sub> (<strong class="boldFont">3strong>) and Hg(Ph<sub>3sub>P)(SCOth)<sub>2sub> (<strong class="boldFont">4strong>) while in chloroform/n-hexane the binary Hg(II) complexes, Hg(SCOPh)<sub>2sub> (<strong class="boldFont">5strong>) and Hg(SCOth)<sub>2sub> (<strong class="boldFont">6strong>) were isolated. In another reaction a heterobimetallic complex, Hg(SCOPh)<sub>2sub>TiCl<sub>4sub> (<strong class="boldFont">7strong>) was obtained as the end product. Molecular structures of <strong class="boldFont">3strong>, <strong class="boldFont">4strong> and <strong class="boldFont">6strong> were studied by single crystal X-ray diffraction. The crystals of <strong class="boldFont">4strong> provided an interesting example of polytopal isomerism. Structures and electronic transitions have been explained on the basis of DFT calculations.