Kirgan Robert, Simpson Megan, Moore Curtis, Day Jeff, Bui Loan, Tanner Clayton, Rillema D Paul
Department of Chemistry, Wichita State University, Wichita, KS 67260-0051, USA.
Inorg Chem. 2007 Aug 6;46(16):6464-72. doi: 10.1021/ic700512j. Epub 2007 Jul 14.
The chloro and pyridinate derivatives of rhenium(I) tricarbonyl complexes containing the diimine ligands 2,2'-bipyrazine (bpz) and 5,5'-dimethyl-2,2'-bipyrazine (Me2bpz) are reported. Absorption maxima occur in the visible and ultraviolet regions of the spectrum; emission is structureless at room temperature and at 77 K; the infrared spectrum consists of three carbonyl stretches; electrochemically, a reversible reduction, an irreversible reduction, and an irreversible oxidation take place. Some ring protons are shielded and others deshielded in the presence of the methyl substituents attached to the bpz ring. DFT and TDDFT calculations provide insight into interpreting electronic and vibrational properties of the complexes. When compared to similar rhenium(I) tricarbonyl complexes of 2,2'-bipyridine (bpy) and 2,2'-bipyrimidine (bpm), the Me2bpz complexes are comparable to bpm derivatives and their properties are intermediate between those of bpy and bpz complexes.
报道了含二亚胺配体2,2'-联吡嗪（bpz）和5,5'-二甲基-2,2'-联吡嗪（Me2bpz）的铼（I）三羰基配合物的氯代和吡啶酸酯衍生物。吸收最大值出现在光谱的可见光和紫外区域；在室温及77 K下发射无结构；红外光谱由三个羰基伸缩振动组成；在电化学方面，发生了一个可逆还原、一个不可逆还原和一个不可逆氧化。在连接到bpz环上的甲基取代基存在的情况下，一些环质子被屏蔽，而另一些则去屏蔽。密度泛函理论（DFT）和含时密度泛函理论（TDDFT）计算有助于深入理解配合物的电子和振动性质。与2,2'-联吡啶（bpy）和2,2'-联嘧啶（bpm）的类似铼（I）三羰基配合物相比，Me2bpz配合物与bpm衍生物相当，其性质介于bpy和bpz配合物之间。
