The Dramatic Influence of Diamidoamine Ligands on the Structure and Reactivity of Low-Valent Tin and Bismuth Derivatives

Fauré, Jean-Luc; Réau, Régis; Bertrand, Guy

doi:10.1002/(sici)1099-0682(199912)1999:12<2295::aid-ejic2295>3.3.co;2-6

Cited by 21 publications

(44 citation statements)

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“…5) a three-centered four-electron bond with the participation of vacant 4p z orbital of Ge atom is formed in Br/Ge)N fragment. Halogenation of "heavy carbenes" may be occurred by action of others reagents (for example BiCl 3 [18]). For the first time we investigate reaction of germylenes with GeCl 4 .…”

Section: Reactions With Changing Of Germanium Oxidation Statementioning

confidence: 99%

Stabilized germylenes based on dialkanolamines: Synthesis, structure, chemical properties

Huang

Kireenko

Zaitsev

et al. 2012

Journal of Organometallic Chemistry

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Section: Reactions With Changing Of Germanium Oxidation Statementioning

confidence: 99%

Stabilized germylenes based on dialkanolamines: Synthesis, structure, chemical properties

Huang

Kireenko

Zaitsev

et al. 2012

Journal of Organometallic Chemistry

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“…This conclusion is confirmed by the experimental data: the only compound from this class studied by X ray diffraction analysis, A9Sn, is a monomer in the solid phase. 20 The bond lengths in A9Sn are given below for comparison: N-Sn, 2.082(5), 2.117(6) Å; N→Sn, 2.323(6) Å (X ray diffraction data 20 ); N-Sn, 2.133, 2.161 Å; N→Sn, 2.449 Å (results of calculations). The calculated bond lengths exceed the experimental values (X ray date), thus reflecting the crystal pack ing effects.…”

Section: Resultsmentioning

confidence: 99%

Structures of germylenes and stannylenes with chelating ligands: a DFT study

et al. 2009

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Geometries of 20 germylenes and 18 stannylenes based on dialkanolamines, diethylenetri amines, and related compounds were optimized by the DFT method. It was found that the most of the germylenes and stannylenes studied are more stable as dimeric structures of different types. The dimerization is possible due to either additional Ge-O(N) interactions or Ge-Ge bonding. The factors leading to the stabilzation of one or another isomer are examined.Presently, investigation of compounds containing di valent Group 14 elements (Si, Ge, Sn, Pb) is a rapidly developing area of organometallic chemistry. "Heavy" car benes can be the starting substances for the synthesis of diverse organometallic compounds and intermediates, for instance, transition metal complexes and clusters, deriva tives with the metal-carbon and metal-heteroatom mul tiple bonds, small metallacycles, and analogs of carbeni um ions and radicals. Approaches to the synthesis of these compounds and studies of their reactivity were analyzed in reviews. 1-8 It is well known that such compounds (mainly silicon and germanium derivatives, and, to a lesser extent, tin compounds) are not so stable as their analogs contain ing metal atoms with the formal oxidation state +4.Several possible methods for stabilization of such com pounds have been reported to date. 2 The first method, viz., kinetic stabilization, assumes the insertion of bulky sub stituents that impede the approach of the reactant to the reaction center of the molecule into the groups bound to the germanium atom. The second and third methods, viz., thermodynamic stabilization, are realized for compounds in which (a) the metal atom is covalently bound to n or π donor substituents and (b) there is an additional tran sannular interaction with an electron donor.Therefore, diethanolamines RN(CH 2 CH 2 OH) 2 and diethylenetriamines RN(CH 2 CH 2 NR´H) 2 capable of forming three bonds (two covalent bonds and one coordi nation bond) with the metal atom seem to be appropriate ligands for stabilization of germylenes and stannylenes. Earlier, 8-16 it was found that dialkanolamines readily form compounds with germanium and tin atoms in the oxida tion state +4. However, analysis of literature data showed that such ligands were almost not used in chemistry of "heavy" carbenes, although they are suitable for efficient stabilization of the electron unsaturated center by all the three methods mentioned above, and the kinetic stabiliza tion is not excluded even in the case of dialkanolamines if the carbon atoms have bulky substituents.The syntheses of one germylene, MeN(CH 2 CH 2 O) 2 Ge, 17 and several stannylenes 18,19 were reported. The struc tures of these compounds were not studied by X ray dif fraction analysis. In addition, two stannylenes, MeN(CH 2 CH 2 NPr i ) 2 Sn and MeN(CH 2 CH 2 NSiMe 3 ) 2 Sn, were synthesized. The structure of the latter compound was studied 20 by X ray diffraction analysis. A series of works 21-25 on the synthesis of the Ge 2+ and Sn 2+ deriva tives based on Me 2 NCH 2 CH 2 OH suggest the ...

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“…Dichloro-substituted stannocanes can also be obtained as a result of oxidation-reduction reactions with tin tetrachloride [1] or bismuth(III) chloride [44].…”

Section: W-y 3stmentioning

confidence: 99%