scholarly journals Complexes of Dichlorogermylene with Phosphine/Sulfoxide-Supported Carbone as Ligand

Molecules ◽  
2021 ◽  
Vol 26 (7) ◽  
pp. 2005
Author(s):  
Ugo Authesserre ◽  
Sophie Hameury ◽  
Aymeric Dajnak ◽  
Nathalie Saffon-Merceron ◽  
Antoine Baceiredo ◽  
...  
Keyword(s):  
Solid State ◽  
Nmr Spectroscopy ◽  
Carbon Atom ◽  
Diffraction Analysis ◽  
Coordination Complexes ◽  
X Ray Diffraction ◽  
X Ray ◽  
Central Carbon Atom ◽  
Lone Pairs ◽  
Central Carbon

Due to their remarkable electronic features, recent years have witnessed the emergence of carbones L2C, which consist in two donating L ligands coordinating a central carbon atom bearing two lone pairs. In this context, the phosphine/sulfoxide-supported carbone 4 exhibits a strong nucleophilic character, and here, we describe its ability to coordinate dichlorogermylene. Two original stable coordination complexes were obtained and fully characterized in solution and in the solid state by NMR spectroscopy and X-ray diffraction analysis, respectively. At 60 °C, in the presence of 4, the Ge(II)-complex 5 undergoes a slow isomerization that transforms the bis-ylide ligand into an yldiide.

A new aspect of the “pseudo water” concept of bis(trimethylsilyl)carbodiimide – “pseudohydrates” of aluminum

2018 ◽  
Vol 73 (11) ◽  
pp. 911-918
Author(s):  
Katrin Krupinski ◽  
Erica Brendler ◽  
Robert Gericke ◽  
Jörg Wagler ◽  
Edwin Kroke
Keyword(s):  
Solid State ◽  
Nmr Spectroscopy ◽  
Diffraction Analysis ◽  
Quantum Chemical ◽  
Metal Salt ◽  
Similar Group ◽  
X Ray Diffraction ◽  
X Ray ◽  
Positional Disorder ◽  
Cp Mas Nmr

AbstractBis(trimethylsilyl)carbodiimide (BTSC), so-called “pseudo water” because of some analogies such as similar (group)electronegativities of Me3Si– vs. H– and –N=C=N– vs. –O–, may form two different kinds of “pseudo hydrates” of metals (M), i.e. M–N(SiMe3)=C=N(SiMe3) and M–N≡C–N(SiMe3)2, derived from its carbodiimide and cyanamide isomeric forms, respectively. With anhydrous AlCl3 in Me3SiCl solution BTSC was shown to be capable of forming both kinds of solvates, i.e. Cl3Al–N(SiMe3)–C≡N(SiMe3) (1) and ((Cl3Al)(Me3Si)NCN)3–Al–(N≡C–N(SiMe3)2)3 (2). Both compounds were isolated as crystalline solids, which undergo condensation reactions upon storage. By single-crystal X-ray diffraction analysis the constitution of 1 was confirmed unambiguously, and quantum chemical calculations (B3LYP/6-311++g(d,p)) confirmed that compound 1 is 6 kcal mol−1 more stable than its hypothetical N,N-bis(trimethylsilyl)cyanamide isomer Cl3Al–N≡C–N(SiMe3)2. Compound 1 represents the first crystallographically confirmed disilylcarbodiimide complex of a metal salt. The molecules of compound 2 are heavily disordered in the solid state (positional disorder of N≡C–N(SiMe3)2 vs. N≡C–N(SiMe3)(AlCl3) and positional disorder of SiMe3 vs. AlCl3 groups in the latter). Therefore, the identity of 2 was additionally confirmed by 13C, 15N, 27Al and 29Si CP/MAS NMR spectroscopy.

III. Thioanalogs of Sparteine Lactams. (+)-17-Thionosparteine and its Perchlorate Salt

2002 ◽  
Vol 57 (5) ◽  
pp. 563-570 ◽  
Author(s):  
Waleria Wysocka ◽  
Renata Kolanoś ◽  
Teresa Borowiak ◽  
Grzegorz Dutkiewicz
Keyword(s):  
Solid State ◽  
Nmr Spectroscopy ◽  
Diffraction Analysis ◽  
X Ray Diffraction ◽  
X Ray ◽  
Conformational Rigidity ◽  
Ir And Nmr Spectroscopy ◽  
Perchlorate Salt

(+)-17-Thionosparteine and its perchlorate have been obtained and characterized by IR and NMR spectroscopy as well as by X-ray diffraction analysis. Introduction of the thiolactam group into the cis-quinolizidine system causes conformational rigidity of this fragment. Moreover, the conformations in solution and in the solid state are the same.

Ten-Vertex Polyhedral Monocarbaborane Chemistry. The Novel High-Yield Formation of the Ten-Vertex closo Compound [6-(PMe2Ph)-closo-1-CB9H9] from the Thermolysis of [8,8-(PMe2Ph)2-nido-8,7-PtCB9H11]

1993 ◽  
Vol 58 (12) ◽  
pp. 2924-2935 ◽  
Author(s):  
Jane H. Jones ◽  
Bohumil Štíbr ◽  
John D. Kennedy ◽  
Mark Thornton-Pett
Keyword(s):  
Nmr Spectroscopy ◽  
Diffraction Analysis ◽  
High Yield ◽  
Monoclinic Space Group ◽  
The Novel ◽  
X Ray Diffraction ◽  
Metal Centre ◽  
X Ray ◽  
Yield Formation ◽  
Boiling Toluene

Thermolysis of [8,8-(PMe2Ph)2-nido-8,7-PtCB9H11] in boiling toluene solution results in an elimination of the platinum centre and cluster closure to give the ten-vertex closo species [6-(PMe2Ph)-closo-1-CB9H9] in 85% yield as a colourles air stable solid. The product is characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis. Crystals (from hexane-dichloromethane) are monoclinic, space group P21/c, with a = 903.20(9), b = 1 481.86(11), c = 2 320.0(2) pm, β = 97.860(7)° and Z = 8, and the structure has been refined to R(Rw) = 0.045(0.051) for 3 281 observed reflections with Fo > 2.0σ(Fo). The clean high-yield elimination of a metal centre from a polyhedral metallaborane or metallaheteroborane species is very rare.

scholarly journals Reactions of Dihaloboranes with Electron-Rich 1,4-Bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadienes

Molecules ◽  
2020 ◽  
Vol 25 (12) ◽  
pp. 2875
Author(s):  
Li Ma ◽  
Xiaolin Zhang ◽  
Wenbo Ming ◽  
Shengxin Su ◽  
Xiaoyong Chang ◽  
...  
Keyword(s):  
Double Bond ◽  
Nmr Spectroscopy ◽  
Diffraction Analysis ◽  
1H Nmr Spectroscopy ◽  
Variable Temperature ◽  
Organosilicon Compounds ◽  
X Ray Diffraction ◽  
X Ray ◽  
Multinuclear Nmr Spectroscopy ◽  
Bond Character

The reactions of electron-rich organosilicon compounds 1,4-bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene (1), 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene (2), and 1,1′-bis(trimethylsilyl)-1,1′-dihydro-4,4′-bipyridine (12) with B-amino and B-aryl dihaloboranes afforded a series of novel B=N-bond-containing compounds 3–11 and 13. The B=N rotational barriers of 7 (>71.56 kJ/mol), 10 (58.79 kJ/mol), and 13 (58.65 kJ/mol) were determined by variable-temperature 1H-NMR spectroscopy, thus reflecting different degrees of B=N double bond character in the corresponding compounds. In addition, ring external olefin isomers 11 were obtained by a reaction between 2 and DurBBr2. All obtained B=N-containing products were characterized by multinuclear NMR spectroscopy. Compounds 5, 9, 10a, 11, and 13a were also characterized by single-crystal X-ray diffraction analysis.

Imidazole-containing Bispidine Ligands: Synthesis, Structure and Cu(II) Complexation

2011 ◽  
Vol 66 (7) ◽  
pp. 721-728 ◽  
Author(s):  
Martin Walther ◽  
Madlen Matterna ◽  
Stefanie Juran ◽  
Silke Fähnemann ◽  
Holger Stephan ◽  
...  
Keyword(s):  
Solid State ◽  
Nmr Spectroscopy ◽  
Enol Form ◽  
Trans Configuration ◽  
X Ray Diffraction ◽  
X Ray ◽  
The Impact ◽  
Configurational Isomerism

The preparation and characterization of tris-pyridyl bispidine (3,7-diazabicyclo[3.3.1]nonane) derivatives with benzimidazole and imidazole donor groups at the N-3 position of the bispidine skeleton and their copper(II) complexes are reported. The impact of the hetaryl substituents on the configurational isomerism of piperidones and their corresponding bispidones has been studied by NMR spectroscopy, revealing the exclusive appearance in the enol form for the piperidones in solution and the trans-configuration regarding the two pyridyl substituents, as well as the sole formation of the unsymmetric exo-endo isomers for the corresponding bispidones. Thus, the bispidones are preorganized ligands for building pentacoordinated complexes, confirmed by the preparation and characterization of the corresponding Cu(II) complexes. Of the di-pyridyl piperidones with benzimidazole and imidazole substituents, and of the Cu(II) complex of the benzimidazole-containing bispidone, crystals have become available for the analysis by X-ray diffraction, showing that the piperidones form the enol tautomers also in the solid state.

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