98061-21-3Relevant articles and documents
Cyclometalated Rhodium(III) Complexes Based on Substituted 2-Phenylpyridine Ligands: Synthesis, Structures, Photophysics, Electrochemistry, and DNA-Binding Properties
Liang, Haoran,Hao, Taotao,Yin, Changzhen,Yang, Xi,Fu, Haiyan,Zheng, Xueli,Li, Ruixiang,Xiao, Dan,Chen, Hua
, p. 4149 - 4157 (2017)
A new series of octahedral rhodium(III) complexes 1–8 of the type [(Ln)2Rh(dppz)]Cl (n = 1–6) and [(Ln)2Rh(dppz)](PF6) {n = 1, 7, 8; L = 2-phenylpyridine, with different modifications, as the C,N-chelating ligand; and dppz = dipyrido[3,2-a:2′,3′-c]phenazine} have been synthesized and fully characterized. The photophysical properties of the complexes have been investigated. The single-crystal X-ray diffraction structures of five complexes – [(L1)2Rh(dppz)](PF6), [(L2)2Rh(dppz)]Cl, [(L3)2Rh(dppz)](PF6), [(L4)2Rh(dppz)](PF6), and [(L8)2Rh(dppz)](PF6) – have confirmed the anticipated structure and have revealed the effect of substitution on the structure of the complex, which has been reasonably explained through experimental electrochemical characterization. The interaction of complexes 1–8 with calf thymus DNA (CT DNA) has been verified by the fluorescent detection of ethidium bromide (EB) displacement studies. The result clearly suggests that the DNA-binding abilities of these Rh complexes are not only influenced by the DNA-intercalator dppz, but are also highly influenced by the electronic and steric properties of the C,N-chelating ligands.
Cp*Rh(iii)/boron hybrid catalysis for directed C-H addition to β-substituted α,β-unsaturated carboxylic acids
Hirata, Yuki,Kojima, Masahiro,Matsunaga, Shigeki,Tanaka, Ryo,Yoshino, Tatsuhiko
supporting information, p. 76 - 79 (2021/12/29)
The C-H bond addition reaction of 2-phenylpyridine derivatives with α,β-unsaturated carboxylic acids catalyzed by Cp*Rh(iii)/BH3·SMe2is reported. Activation of C-H bonds with the rhodium catalyst and activation of α,β-unsaturated carboxylic acids with the boron catalyst cooperatively work, and a BINOL-urea hybrid ligand significantly improved the reactivity. With the optimized hybrid catalytic system, various β-disubstituted carboxylic acids were obtained under mild reaction conditions.
N-heterocyclic carbene enabled rhodium-catalyzed ortho C(sp2)-H borylation at room temperature
Zhong, Lei,Zong, Zhi-Hong,Wang, Xi-Cun
supporting information, p. 2547 - 2552 (2019/03/27)
We report a rhodium-catalyzed ortho C(sp2)-H borylation of 2-phenylpyridines using commercially available N-heterocyclic carbenes (NHCs) as ligand and pinacolatodiboron (B2pin2) as borylating reagent. The reaction could take place at room temperature, tolerating a wide range of functionalities and affording ortho borylated products in moderate to excellent yields. The current method is also applicable to gram-scale reaction with reduced catalyst loading.
Ruthenium-Catalyzed Reductive Cleavage of Unstrained Aryl-Aryl Bonds: Reaction Development and Mechanistic Study
Zhu, Jun,Chen, Peng-hao,Lu, Gang,Liu, Peng,Dong, Guangbin
supporting information, p. 18630 - 18640 (2019/11/21)
Cleavage of carbon-carbon bonds has been found in some important industrial processes, for example, petroleum cracking, and has inspired development of numerous synthetic methods. However, nonpolar unstrained C(aryl)-C(aryl) bonds remain one of the toughest bonds to be activated. As a detailed study of a fundamental reaction mode, here a full story is described about our development of a Ru-catalyzed reductive cleavage of unstrained C(aryl)-C(aryl) bonds. A wide range of biaryl compounds that contain directing groups (DGs) at 2,2′ positions can serve as effective substrates. Various heterocycles, such as pyridine, quinoline, pyrimidine, and pyrazole, can be employed as DGs. Besides hydrogen gas, other reagents, such as Hantzsch ester, silanes, and alcohols, can be employed as terminal reductants. The reaction is pH neutral and free of oxidants; thus a number of functional groups are tolerated. Notably, a one-pot C-C activation/C-C coupling has been realized. Computational and experimental mechanistic studies indicate that the reaction involves a ruthenium(II) monohydride-mediated C(aryl)-C(aryl) activation and the resting state of the catalyst is a η4-coordinated ruthenium(II) dichloride complex, which could inspire development of other transformations based on this reaction mode.
