Hypervalent Compounds of Organic Germanium, Tin and Lead Derivatives

Baukov, Yuri I.; Tandura, S. N.

doi:10.1002/chin.200346246

Cited by 11 publications

(14 citation statements)

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“…Heavier Group 14 elements such as silicon and tin are known to readily form hypervalent compounds through donor!acceptor interactions with organic Lewis bases. [11][12][13] A related situation is envisioned in complexes C, with a transition metal acting as a Lewis base. Such donor!…”

mentioning

confidence: 99%

Gold–Silane and Gold–Stannane Complexes: Saturated Molecules as σ‐Acceptor Ligands

et al. 2009

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mentioning

confidence: 99%

Gold–Silane and Gold–Stannane Complexes: Saturated Molecules as σ‐Acceptor Ligands

et al. 2009

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“…Aside from such synthetic applications, an interesting aspect of organotin(IV) compounds is their structural diversity. Organotin(IV) compounds often form structures in which previously tetravalent Sn atoms exhibit the coordination number greater than four, that is, the Sn atoms become hypervalent [1,8,9]. In such cases, the Sn atoms are involved in additional inter-and/or intramolecular interactions that expand their coordination number and, consequently, change their tetrahedral configuration.…”

Section: Introductionmentioning

confidence: 99%

“…The appearance of such additional interactions results from the pronounced electron-acceptor ability of the Sn atoms and, in the presence of electron donors D, it leads to the formation of dative D → Sn bonds (also known as coordination bonds). Nitrogen, oxygen, and halogen atoms are most often the electron donors as they can easily provide a lone electron pair to the Sn atom [9].…”

Section: Introductionmentioning

confidence: 99%

Theoretical investigation of the N → Sn coordination in (Me3SnCN)2

Matczak

2014

Struct Chem

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The N → Sn coordination occurring in the (Me 3 SnCN) 2 dimer has been investigated using various computational methods and several theoretical tools possessing great interpretative potential. The dimer is formed by moving the C≡N fragment of the first Me 3 SnCN molecule close to the Sn atom of the second molecule and the resulting N → Sn coordination corresponds to that observed in the crystal structure of trimethyltin cyanide. The geometry of (Me 3 SnCN) 2 is optimized using the MP2 method and its 11 variants, and then it is compared with the reference geometry obtained at the CCSD level of theory. SCS-MP2 reproduces best the reference geometry of (Me 3 SnCN) 2 and its accuracy is close to that of the MP4 (SDQ) method. Two families of basis sets, namely the correlation-consistent basis sets proposed by Dunning and co-workers and the 'def2' basis sets developed by Ahlrichs and co-workers, are taken into account and their effect on the geometry of the dimer is examined in detail. The intermolecular interaction in (Me 3 SnCN) 2 has been analyzed using SAPT, NBO, QTAIM, and ELF. The results indicate that the (Me 3 SnCN) 2 dimer possesses a weak N → Sn coordination bond whose character is predominantly ionic. A value of −7.64 kcal/mol is proposed to be the best estimate of the interaction energy between the Me 3 SnCN molecules in the dimer.

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“…[2,18] However, only three of these structures contain an ethynylgermatrane fragment (phenylethynylgermatrane, and its CHCl 3 solvate, and 4-fluorophenylethynyl analogue [5,6,8] ). These compounds are characterized by transannular NǞGe distances of 2.178, 2.160, and 2.175 Å , respectively, which are short in comparison with those in other alkyl-, alkenyl-, and arylgermatranes (2.20Ϫ2.24 Å ).…”

Section: Molecular Structures Of the Germatranesmentioning

confidence: 99%

Synthesis, Structure and Chemical Transformations of Ethynylgermatranes

et al. 2003

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Ethynylgermatranes have been prepared from monosubstituted acetylenes by a three‐step synthesis without isolation of the hydrolytically unstable intermediate chlorogermanes and ethoxygermanes. Boiling an equimolar mixture of tetrachlorogermane Cl4Ge, acetylene RC≡CH and triethylamine in hexane leads to germylation of the Csp−H bond and the formation of ethynyl‐substituted trichlorogermanes. Subsequent alkoxylation of chlorogermanes by ethanol in the presence of triethylamine affords triethoxygermanes that then take part in transalkoxylation with triethanolamine to give ethynylgermatranes. The molecular structures of all ethynylgermatranes and the hexacarbonyldicobalt complex of 1‐heptynylgermatrane have been determined by X‐ray crystallography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Hypervalent Compounds of Organic Germanium, Tin and Lead Derivatives

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 11 publications

References 1 publication

Gold–Silane and Gold–Stannane Complexes: Saturated Molecules as σ‐Acceptor Ligands

Gold–Silane and Gold–Stannane Complexes: Saturated Molecules as σ‐Acceptor Ligands

Theoretical investigation of the N → Sn coordination in (Me3SnCN)2

Synthesis, Structure and Chemical Transformations of Ethynylgermatranes

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