scholarly journals 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)

Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1321
Author(s):  
Yasunobu Asawa ◽  
Aleksandra V. Arsent’eva ◽  
Sergey A. Anufriev ◽  
Alexei A. Anisimov ◽  
Kyrill Yu. Suponitsky ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Single Crystal ◽  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
X Ray Diffraction ◽  
Stable Conformation ◽  
Acyl Chlorides ◽  
X Ray ◽  
Cesium Fluoride ◽  
The Stability

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.

scholarly journals 6,6′-Dimethyl-1,1′,5,5′-tetraaza-6,6′-bi(bicyclo[3.1.0]hexane): synthesis and investigation of molecular structure by quantum-chemical calculations, NMR spectroscopy and X-ray diffraction analysis

2021 ◽  
Author(s):  
Inna Nikolaevna Kolesnikova ◽  
Vladimir Vladimirovich Kuznetsov ◽  
Alexander Sergeevich Goloveshkin ◽  
Nikolai Andreevich Chegodaev ◽  
Nina Nikolaevna Makhova ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Nmr Spectroscopy ◽  
Diffraction Analysis ◽  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
X Ray Diffraction ◽  
X Ray

scholarly journals Synthesis and Structure of Methylsulfanyl Derivatives of Nickel Bis(Dicarbollide)

Molecules ◽  
2019 ◽  
Vol 24 (24) ◽  
pp. 4449 ◽  
Author(s):  
Sergey A. Anufriev ◽  
Kyrill Yu. Suponitsky ◽  
Oleg A. Filippov ◽  
Igor B. Sivaev
Keyword(s):  
Hydrogen Bonds ◽  
Single Crystal ◽  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
X Ray Diffraction ◽  
Gauche Conformation ◽  
X Ray ◽  
Derivatives Of ◽  
Transoid Conformation

Symmetrically and unsymmetrically substituted methylsulfanyl derivatives of nickel(III) bis(dicarbollide) (Bu4N)[8,8′-(MeS)2-3,3′-Ni(1,2-C2B9H10)2], (Bu4N)[4,4′-(MeS)2-3,3′-Ni(1,2-C2B9H10)2], and (Bu4N)[4,7′-(MeS)2-3,3′-Ni(1,2-C2B9H10)2] were synthesized, starting from [Ni(acac)2]3 and the corresponding methylsulfanyl derivatives of nido-carborane (Bu4N)[10-MeS-7,8-C2B9H11] and (Bu4N)[10-MeS-7,8-C2B9H11]. Structures of the synthesized metallacarboranes were studied by single-crystal X-ray diffraction and quantum chemical calculations. The symmetrically substituted 8,8′-isomer adopts transoid conformation stabilized by two pairs of intramolecular C–H···S hydrogen bonds between the dicarbollide ligands. The unsymmetrically substituted 4,7′-isomer adopts gauche conformation, which is stabilized by two nonequivalent C–H···S hydrogen bonds and one short chalcogen B–H···S bond (2.53 Å, −1.4 kcal/mol). The gauche conformation was found to be also preferred for the 4,7′-isomer.

Syntheses and structures of benzo-bis(1,3,2-diazaboroles) and acenaphtho-1,3,2-diazaboroles

2019 ◽  
Vol 48 (45) ◽  
pp. 16911-16921 ◽  
Author(s):  
Lothar Weber ◽  
Daniel Eickhoff ◽  
Anna Chrostowska ◽  
Alain Dargelos ◽  
Clovis Darrigan ◽  
...  
Keyword(s):  
Single Crystal ◽  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
Electron Systems ◽  
X Ray Diffraction ◽  
X Ray

1,3,2-Diazaboroles 4 and 7 with extended π-electron systems were synthesised and characterised by single crystal X-ray diffraction and quantum-chemical calculations.

Hungry for charge – how a beryllium scorpionate complex “eats” a weakly coordinating anion

2020 ◽  
Vol 75 (5) ◽  
pp. 503-508
Author(s):  
Dominik Naglav-Hansen ◽  
Kevin Dzialkowski ◽  
Briac Tobey ◽  
Christoph Wölper ◽  
Georg Jansen ◽  
...  
Keyword(s):  
Nmr Spectroscopy ◽  
Single Crystal ◽  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
X Ray Diffraction ◽  
X Ray ◽  
Multinuclear Nmr Spectroscopy ◽  
Weakly Coordinating ◽  
Weakly Coordinating Anion ◽  
Heteroleptic Complex

AbstractWe present the reaction of a tris(pyrazolyl) beryllium scorpionate (TpBe) complex with a weakly coordinating anion (WCA), which yields the heteroleptic complex TpBeOC(CF3)31 (TpBeORF). The product 1 has been characterized by multinuclear NMR spectroscopy (1H, 9Be, 13C) and single-crystal X-ray diffraction (scXRD). Quantum chemical calculations (DFT, NPA, LOL) were performed to study the bonding nature in 1.

1,2-Hydroboration of Alkyn-1-yldichlorosilanes using Triethylborane

2008 ◽  
Vol 63 (11) ◽  
pp. 1267-1275 ◽  
Author(s):  
Bernd Wrackmeyer ◽  
Ezzat Khan ◽  
Wolfgang Milius
Keyword(s):  
Molecular Structure ◽  
Single Crystal ◽  
Hydrogen Transfer ◽  
X Ray Diffraction ◽  
X Ray ◽  
Ethyl Group ◽  
Nmr Data

Abstract Triethylborane, BEt3, can act as a 1,2-hydroborating reagent towards alkyn-1-ylsilanes, depending on the nature of the silane. A mechanism is proposed invoking hydrogen transfer from the β -carbon of one ethyl group, quite different from the 1,2-hydroboration mechanism using tri-n-propylborane, BnPr3. The structure of the products has been confirmed by comparison with that obtained using 9-borabicyclo[3.3.1]nonane, 9-BBN, as a well established 1,2-hydroborating reagent. All products have been characterized by a consistent set of NMR data (1H, 11B, 13C and 29Si NMR). The molecular structure of (Z)-1-dichlorosilyl-1-[9-(9-borabicyclo[3.3.1]nonyl)]-2-phenylethene has been determined by single crystal X-ray diffraction.

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