Si(CH2CH2SnH3)4—a unique organotin hydride featuring 12 SnH units in a dendritic molecule. Single-crystal X-ray structures of tetrakis(2-stannylethylene)silane and tetrakis[2-(triphenylstannyl)ethylene]silane

Schumann, Herbert; Wassermann, Birgit C.; Frackowiak, Michaela; Omotowa, Bamidele A.; Schutte, Stefan; Velder, Janna; Mühle, Stefan H.; Krause, W.

doi:10.1016/s0022-328x(00)00188-1

Cited by 24 publications

(21 citation statements)

References 40 publications

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“…These values are lower than in the simple organostannane Si(CH 2 CH 2 SnH 3 ) 4 , where ν(SnH) is found at 1852 cm -1 . 65 A similar observation has been made for another transitionmetal-substituted stannane, Cp 2 Hf(SnHMes 2 )Cl, where ν(SnH) is 1728 cm -1 , whereas the value for Mes 2 SnH 2 is 1864 cm -1 . 66 In the 1 H NMR the SnH 3 protons are seen as a triplet at 2.86 ppm through coupling to two equivalent phosphorus atoms ( 3 J PH ) 3.2 Hz) with Sn satellites ( 1 J 119 SnH ) 1348, 1 J 117 SnH ) 1288 Hz).…”

Section: Snh 3 and Related Ligands From Reactions With Hydride Nucsupporting

confidence: 62%

“…These one-bond Sn-H coupling constants are conspicuously lower than those observed in simple organostannanes, R n SnH 4-n (n ) 1-3), which are typically 1900-1600 Hz. 65,67 Even lower values, 961 and 918 Hz, have been recorded for Cp 2 Hf(SnHMes 2 )Cl. 66 As expected, the Sn-H bonds are quite reactive, and dissolution in chloroform converts 75 to the corresponding trichlorostannyl complex Os(SnCl 3 )(κ 2 -S 2 CNMe 2 )(CO)(PPh 3 ) 2 (76), while reaction with HF gives the corresponding trifluorostannyl complex Os(SnF 3 )(κ 2 -S 2 CNMe 2 )(CO)(PPh 3 ) 2 (77) (see Scheme 27).…”

Section: Snh 3 and Related Ligands From Reactions With Hydride Nucmentioning

confidence: 96%

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Similarities and Contrasts between Silyl and Stannyl Derivatives of Ruthenium and Osmium

Roper

Wright

2006

Organometallics

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Silyl and stannyl complexes of ruthenium and osmium bearing halogen substituents on the silicon and tin atoms undergo many interesting reactions. While there are formal similarities, there are also marked differences between these silyl and stannyl derivatives. This review first surveys the synthetic approaches we have developed to the silyl and stannyl complexes that involve oxidative addition of halogenated silanes coupled with reductive elimination for the preparation of the silyl complexes L n M(SiR n X 3-n ) (M ) Ru, Os) and reaction between L n MH and the vinylstannane R 3 SnCHdCH 2 to give first the triorganostannyl complexes L n M(SnR 3 ) (M ) Ru, Os), which are then functionalized by redistribution reactions to give L n M(SnR n X 3-n ) (M ) Ru, Os). Among the unusual compounds derived from these halogenated silyl and stannyl complexes are derivatives with the following novel ligands: Si(OH) 3 , Sn-(OH) 3 , silatranyl, stannatranyl, SnH 3 , and SnMe 2 SnPh 3 . A contrast between the osmasilanol L n Os(SiMe 2 -OH) and the osmastannol L n Os(SnMe 2 OH) is that the former deprotonates to a silanolate anion, [L n Os(SiMe 2 O)] -, while the latter, when treated with base, ortho-stannylates a triphenylphosphine ligand. Another contrast is provided by the ease with which osmium trimethylstannyl complexes undergo R-methyl migration reactions.

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Section: Snh 3 and Related Ligands From Reactions With Hydride Nucsupporting

confidence: 62%

Section: Snh 3 and Related Ligands From Reactions With Hydride Nucmentioning

confidence: 96%

Similarities and Contrasts between Silyl and Stannyl Derivatives of Ruthenium and Osmium

Roper

Wright

2006

Organometallics

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“…There is scarce structural evidence of short intermolecular contacts involving SnH bonds. The shortest SnH···HSn distances found are 2.664 Å in the crystal structure of tetrakis(2‐stannylethyl)silane (lovfad), and 2.995 Å in that of SnD 4 (173482), to be compared with twice the van der Waals radius of hydrogen, 2.40 Å. All other SnH···HSn distances are longer than 3.25 Å.…”

Section: Structural Analysismentioning

confidence: 84%

Intermolecular interactions in group 14 hydrides: Beyond CH···HC contacts

2017

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In line with previous work in which we established the factors that enhance attractive CH···HC dihydrogen interactions in alkanes, an extended theoretical analysis of noncovalent intermolecular interactions in group 14 hydrides is presented here. Remarkably, these weak interactions may play a major role in determining the crystal structures adopted by several families of molecules. A combined structural and computational analysis at the MP2 level allowed us to identify and characterize different interactions of the type EH···HE and E···HE (E = Si, Ge, Sn, and Pb), and to find also the most suitable scenario for the establishment of each particular type. The nature of the interactions has been analyzed in terms of natural charges of the atoms involved and a topological analysis of the electron density of several dimers confirms the existence of H···H and H···E attractive contacts. We have observed that the interaction strength increases when descending down the periodic group and that silicon has a marked tendency to establish Si···HSi interactions. A size‐dependent backbone effect that reinforces H···H dihydrogen interactions in polyhedral systems has also been found.

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“…Although a few triorganotin derivatives which can be classified as dendrimers have already been described, they have not been prepared under the perspective of dendrimer synthesis, but studied in relation to multinuclear NMR spectroscopic investigations [16]. In preceding papers [17,18] we reported on the synthesis of tin containing metallodendrimers and their functionalization with water-soluble ligands with regard to application as X-ray contrast agents. Continuing our interest in organotin dendrimers we report here the synthesis and spectroscopic characterization of dendrimers with tin atoms as branching units, which can be used as suitable starting materials for new dendritic organotin macromolecules with reactive units on the periphery because they permit multiple possibilities for derivatization.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of some organo-all-tin dendrimers with different peripheral substituents

Schumann

Aksu

Wassermann

2006

Journal of Organometallic Chemistry

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Si(CH2CH2SnH3)4—a unique organotin hydride featuring 12 SnH units in a dendritic molecule. Single-crystal X-ray structures of tetrakis(2-stannylethylene)silane and tetrakis[2-(triphenylstannyl)ethylene]silane

Cited by 24 publications

References 40 publications

Similarities and Contrasts between Silyl and Stannyl Derivatives of Ruthenium and Osmium

Similarities and Contrasts between Silyl and Stannyl Derivatives of Ruthenium and Osmium

Intermolecular interactions in group 14 hydrides: Beyond CH···HC contacts

Synthesis and characterization of some organo-all-tin dendrimers with different peripheral substituents

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