羟基取代邻位碳硼烷引发半夹心金属配合物的区域选择性 B-H/C-H 活化和金属-金属键形成。

Regioselective B-H/C-H activation and metal-metal bond formation induced by half-sandwich metals complexes at hydroxy-substituted o-carboranes.

机构信息

Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Fudan University, Shanghai 200433, P. R. China.

出版信息

Dalton Trans. 2018 Oct 2;47(38):13641-13646. doi: 10.1039/c8dt03104e.

DOI:10.1039/c8dt03104e

PMID:30207352

Abstract

A binuclear iridium complex, (Cp2*Ir2(CH2O)C2B10H8) (6), with a unique metal-metal bond has been synthesized and fully characterized. Importantly, this complex is constructed via selective C-H and B(3)-H bond activation on the carborane precursor. Additionally, when the proligand (2-pyridine)(o-carboranyl)methanol ligand was combined with a half-sandwich iridium complex, selective B(6)-H bond activation or metal-carbon bond formation can be induced by the use of different bases. And the rhodium complex constructed from (2-pyridine)(o-carboranyl)methanol ligand containing a metal-carbon bond has been obtained and fully characterized.

摘要

双核铱配合物(Cp2*Ir2(CH2O)C2B10H8)(6)，具有独特的金属-金属键，已被合成并进行了充分的表征。重要的是，该配合物是通过对前体碳硼烷的选择性 C-H 和 B(3)-H 键活化构建的。此外，当将前配体(2-吡啶)(o-碳硼烷)甲醇配体与半三明治铱配合物结合使用时，通过使用不同的碱，可以诱导选择性的 B(6)-H 键活化或金属-碳键形成。并且已经获得并充分表征了由含有金属-碳键的(2-吡啶)(o-碳硼烷)甲醇配体构建的铑配合物。