Facile Deboronation of Some <i>o</i>‐Carboranylamides

Nie, Yong; Wang, Yafeng; Miao, Junjie; Hu, Chunhua; Zhang, Zhenwei; Cui, Yu; Li, Yexin

doi:10.1002/ejic.201700612

Cited by 3 publications

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References 23 publications

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“…Compound 4 crystallizes in the form of a solvate with molecule of hexane (1:1). The bond lengths in the amide fragments (C carb -C(O) 1.527(3) and 1.516(3) Å; C=O 1.231(2) and 1.234(2) Å; C(O)-N 1.332(3) and 1.337(3) Å) are close to those in the known ortho -carboranilamides [ 39 , 40 , 48 ]. The molecular conformation can be described by a set of torsional angles which define geometry of the amide linker and its orientation relative to the cages ( Table S1 ).…”

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confidence: 52%

Synthesis of Bis(Carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 (n = 0, 1) and Attempt of Synthesis of Gadolinium Bis(Dicarbollide)

et al. 2021

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Bis(carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 (n = 0, 1) were prepared by the reactions of the corresponding carboranyl acyl chlorides with ethylenediamine. Crystal molecular structure of 1,1′-μ-(CH2NH(O)C-1,2-C2B10H11)2 was determined by single crystal X-ray diffraction. Treatment of bis(carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 with ammonium or cesium fluoride results in partial deboronation of the ortho-carborane cages to the nido-carborane ones with formation of [7,7′(8′)-μ-(CH2NH(O)C(CH2)n-7,8-C2B9H11)2]2−. The attempted reaction of [7,7′(8′)-μ-(CH2NH(O)CCH2-7,8-C2B9H11)2]2− with GdCl3 in 1,2-dimethoxy- ethane did not give the expected metallacarborane. The stability of different conformations of Gd-containing metallacarboranes has been estimated by quantum-chemical calculations using [3,3-μ-DME-3,3′-Gd(1,2-C2B9H11)2]− as a model. It was found that in the most stable conformation the CH groups of the dicarbollide ligands are in anti,anti-orientation with respect to the DME ligand, while any rotation of the dicarbollide ligand reduces the stability of the system. This makes it possible to rationalize the design of carborane ligands for the synthesis of gadolinium metallacarboranes on their base.

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