1. Synthesis of Bis(Carboranyl)amides 1,1'-μ-(CH 2 NH(O)C(CH 2 ) n -1,2-C 2 B 10 H 11 ) 2 ( n = 0, 1) and Attempt of Synthesis of Gadolinium Bis(Dicarbollide).
- Author
-
Asawa Y, Arsent'eva AV, Anufriev SA, Anisimov AA, Suponitsky KY, Filippov OA, Nakamura H, and Sivaev IB
- Subjects
- Crystallography, X-Ray, Models, Molecular, Molecular Conformation, Molecular Structure, Amides chemistry, Boranes chemistry, Gadolinium chemistry, Organometallic Compounds chemical synthesis
- Abstract
Bis(carboranyl)amides 1,1'-μ-(CH
2 NH(O)C(CH2 )n -1,2-C2 B10 H11 )2 ( n = 0, 1) were prepared by the reactions of the corresponding carboranyl acyl chlorides with ethylenediamine. Crystal molecular structure of 1,1'-μ-(CH2 NH(O)C-1,2-C2 B10 H11 )2 was determined by single crystal X-ray diffraction. Treatment of bis(carboranyl)amides 1,1'-μ-(CH2 NH(O)C(CH2 )n -1,2-C2 B10 H11 )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-(CH2 NH(O)C(CH2 )n -7,8-C2 B9 H11 )2 ]2- . The attempted reaction of [7,7'(8')-μ-(CH2 NH(O)CCH2 -7,8-C2 B9 H11 )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-C2 B9 H11 )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.- Published
- 2021
- Full Text
- View/download PDF