Coordination study of ruthenium(II) complexes containing a mixed donor (P-N) ligand

详细信息    查看全文

• 作者：Chun-Chin Lee ; Yi-Hung Liu ; Shie-Ming Peng ; Pi-Tai Chou ; Jwu-Ting Chen ; Shiuh-Tzung Liu ; ^{stliu@ntu.edu.tw}
• 关键词：Phosphine ; Amine ; Ruthenium ; Ligand substitution ; Mixed donor
• 刊名：Polyhedron
• 出版年：2012
• 出版时间：16 March, 2012
• 年：2012
• 卷：35
• 期：1
• 页码：23-30
• 全文大小：568 K

文摘

A series of ruthenium(II) complexes containing an o-(diphenylphosphino)aniline (P-N) ligand have been prepared to elucidate the geometric coordination isomers and substitution reactions. Thus, [(P-N)RuCl₂(CO)₂] (1), [(P-N)RuCl₂(dmso)₂] (2) and [(P-N)RuCl₂(PPh₃)] (3) were synthesized by the reactions of various Ru(II) precursors with P-N. Treatment of 2 with CH₃CN yielded the substitution product [(P-N)RuCl₂(dmso)(CH₃CN)] (4). The rate of the dmso ligand self-exchange of 2 was investigated, and ¦¤G^{?/sup> was estimated to be 23.7 kcal/mol, whereas ¦¤G?/sup> for the CH₃CN ligand self-exchange of 4 was 25 kcal/mol. Replacement of CO in 1 with dmso directly yielded [(P-N)RuCl₂(dmso)(CO)] (8). Of course, complex 8 could also be prepared by substitutions of 2 and 4 with CO, but through various intermediates. Furthermore, the substitution reaction of 3 with CO and dmso led to the formation of 8, and complexes 2 and 3 were inter-convertible. The stereochemistry of all the Ru(II) complexes has been established by elemental, spectroscopic and X-ray crystal structural analyses.}