Synthesis of pd complexes combined with photosensitizing of a ruthenium(II) polypyridyl moiety through a series of substituted bipyrimidine bridges.: Substituent effect of the bridging ligand on the photocatalytic dimerization of α-methylstyrene
Synthesis of pd complexes combined with photosensitizing of a ruthenium(II) polypyridyl moiety through a series of substituted bipyrimidine bridges.: Substituent effect of the bridging ligand on the photocatalytic dimerization of α-methylstyrene
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DOI：
10.1021/ic0612909
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发表时间：
2007-04-02
影响因子：
4.6
通讯作者：
Akita, Munetaka
中科院分区：
文献类型：
--
作者：
Inagaki, Akiko;Yatsuda, Shinichi;Akita, Munetaka
单核钌配合物和双核钌中心点中心点中心点钯配合物具有一系列2,2'-联嘧啶配体，[(bpy)(2)Ru(L-n)](2+) [L-n = 2,2'-联嘧啶（L1）， 5,5'-二溴-2,2'-联嘧啶（L2）， 5,5'-二溴-2,2'-联嘧啶（L3）， 4,4'-二甲基-2,2'-联嘧啶（L4）]和[(bpy)(2)Ru(L-n)PdL](m+) [L-n = L1-L3；制备了PdL = PdMeCl （m = 2）和PdMe（溶剂）（m = 3）]，并用光谱和晶体学方法对得到的配合物进行了表征。在二联嘧啶配体上引入取代基导致其电化学和光物理性质的实质性差异。用密度泛函理论计算了取代基对基态分子轨道能级的影响。对-甲基苯乙烯催化二聚化反应的活性研究表明，含有br取代联嘧啶配体的Pd配合物比含有甲基取代或非取代联嘧啶配体的Pd配合物活性高得多。
Mononuclear ruthenium complexes and dinuclear Ru center dot center dot center dot Pd complexes having a series of 2,2'-bipyrimidine ligands, [(bpy)(2)Ru(L-n)](2+) [L-n = 2,2'-bipyrimidine (L1), 5,5'-dimethyl-2,2'-bipyrimidine (L2), 5,5'-dibromo-2,2'-bipyrimidine (L3), 4,4'-dimethyl-2,2'-bipyrimidine (L4), and 4,4',6,6'-tetramethyl- 2,2'-bipyrimidine (L5)] and [(bpy)(2)Ru(L-n)PdL](m+) [L-n = L1-L3; PdL = PdMeCl (m = 2) and PdMe(solvent) (m = 3)], are prepared, and the obtained complexes are characterized by means of spectroscopic and crystallographic methods. Introduction of the substituents on the bipyrimidine ligands led to the substantial differences in their electrochemical and photophysical properties. Density functional theory calculations have been performed to understand the substituent effect on the ground-state molecular orbital energy level. Reactivity studies on the catalytic dimerization of alpha-methylstyrene revealed that the Pd complex having a Br-substituted bipyrimidine ligand were much more active than those of the corresponding Pd complexes having methyl-substituted or nonsubstituted bipyrimidine ligands.