Light-induced metastable linkage isomers of transition metal nitrosyls

被引:20
作者
Fomitchev, DV [1 ]
Coppens, P [1 ]
机构
[1] SUNY Buffalo, Dept Chem, Buffalo, NY 14260 USA
基金
美国国家科学基金会;
关键词
light-induced metastable state; linkage isomer; transition metal nitrosyl; X-ray diffraction; photochemistry and photochromism;
D O I
10.1080/02603599908020419
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Previously observed long lived light induced metastable states of transition metal nitrosyl complexes were identified as eta(2) nitrosyl and isonitrosyl linkage isomers. A novel technique combining low temperature X-ray crystallography and photochemistry was used to determine the geometry of the new species. Light-induced side-bound nitrosyl ligands were observed in complexes with the electronic configurations {MNO}(6) and {MNO}(10), using the nomenclature introduced by Enemark and Feltham. The isonitrosyl binding mode was observed only in the {MNO}(6) complexes. The influence of the trans ligand, with respect to NO, on thermal stability of the isonitrosyls was studied in a series of complexes of Ru (II). In general, the isonitrosyl species were found to be more stable in complexes with the weak pi-donor ligand in the trans position. Results of theoretical calculations based on density functional theory indicate that the new linkage isomers correspond to local minima on the electronic ground state potential energy surface.
引用
收藏
页码:131 / 148
页数:18
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