title: Construction of iridium and rhodium cyclometalated macrocycles based on p-carborane and N,N'-donor bridging ligands.
abstract: Six tetranuclear half-sandwich iridium and rhodium complexes bridged by neutral N,N'-donor pyridyl-imine ligands and 1,12-dicarbadodecaborane(12)-1,12-dicarboxylate (p-CDC) were controllably synthesized and fully characterized. The results revealed that the precursors, binuclear complexes [(Cp*M)2{1,4-bis(2-pyridylmethyleneamino)benzene}Cl2][OTf]2 (Cp* = η(5)-pentamethylcyclopentadienyl, M = Ir (2a), Rh (2b)), have different preferential configurations, and tetranuclear complexes [(Cp*M)4{1,4-bis(2-pyridylmethyleneamino)benzene}2(p-CDC)2][OTf]4 (M = Ir (3a), Rh (3b)), which were prepared using monodentate p-carborane dicarboxylate and 2a or 2b, showed highly twisted backbones. Likewise, homologous regular rectangular compounds [(Cp*M)4{1,4-{(2-C5H4N)HC=N}2-2,3,5,6-Me4C6}2(p-CDC)2][OTf]4 (M = Ir (4a), Rh (4b)) and [(Cp*M)4{1,4-{(2-C5H4N)HC=N}2-1,5-naphthalene}2(p-CDC)2][OTf]4 (M = Ir (5a), Rh (5b)) were obtained following a similar synthetic route. X-ray determination confirmed that 4b and 5b have stacking channels as well.
authors.affiliation: Shanghai Key Laboratory of Molecular Catalysis and Innovative Material, Department of Chemistry, Fudan University, Shanghai, 200433, P. R. China. gxjin@fudan.edu.cn.
authors.forename: Xu-Yu
authors.initials: XY
authors.lastname: Shen
authors.forename: Long
authors.initials: L
authors.lastname: Zhang
authors.forename: Yue-Jian
authors.initials: YJ
authors.lastname: Lin
authors.forename: Guo-Xin
authors.initials: GX
authors.lastname: Jin