Sarkar Biprajit, Frantz Stéphanie, Kaim Wolfgang, Duboc Carole
Institut für Anorganische Chemie, Universität Stuttgart, Germany.
Dalton Trans. 2004 Nov 7(21):3727-31. doi: 10.1039/b407611g. Epub 2004 Oct 8.
The radical complexes [(micro-L)Ru(bpy)(2)](3+), [(micro-bmtz)Ru(cym)Cl](+) and [(micro-L)Re(CO)(3)Cl]*(-), where L are 3,6-disubstituted 1,2,4,5-tetrazines such as 3,6-bis(2-pyrimidyl)-1,2,4,5-tetrazine (bmtz) and cym =p-cymene, were studied by X-band EPR in fluid solution and by 285 GHz EPR in glassy frozen solution. A comparison with other transition metal complexes (Cu, Rh, Os, Ir, Pt) involving tetrazine radical ligands reveals that the g anisotropy reflects (i) the pi acceptor effect of the tetrazine substituents, (ii) the competition from ancillary pi acceptor ligands for back donation from the metal, and (iii) the spin-orbit coupling contributions from the transition metal.
研究了自由基配合物[(μ-L)Ru(bpy)(2)](3+)、[(μ-bmtz)Ru(cym)Cl](+)和[(μ-L)Re(CO)(3)Cl]*(-)，其中L为3,6-二取代的1,2,4,5-四嗪，如3,6-双(2-嘧啶基)-1,2,4,5-四嗪(bmtz)，cym =对异丙基苯，通过X波段电子顺磁共振在流体溶液中以及通过285 GHz电子顺磁共振在玻璃态冷冻溶液中进行研究。与其他涉及四嗪自由基配体的过渡金属配合物(Cu、Rh、Os、Ir、Pt)进行比较表明，g各向异性反映了(i)四嗪取代基的π受体效应，(ii)辅助π受体配体对金属反馈给体的竞争，以及(iii)过渡金属的自旋-轨道耦合贡献。
