Catenated Germanium and Tin Oligomers and Polymers

Foucher, Daniel A.

doi:10.1002/9781119235941.ch9

Cited by 12 publications

(4 citation statements)

References 78 publications

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“…Many applications of the organotin(IV) hydrides found in organic synthesis include the radical-based hydrostannylation and sequential reactions of halides or related compounds − and the hydrostannylation of unsaturated molecules such as alkenes, alkynes, and carbonyls. − In materials chemistry, tin hydrides serve as starting materials for polystannanes that exhibit interesting photoelectric properties through dehydrocoupling reactions. − In addition, theoretical studies suggest that tin hydrides (Sn n H m ) are potentially high-temperature superconductors under pressure. , While tin(IV) hydrides have been well documented for their reactivity and applications, the development of low-valent tin(II) hydrides remains limited to few examples due to the relatively weak Sn(II)–H bond that hampers the isolation of such species. The tetravalent species n Bu 3 SnH features a Sn–H bond dissociation enthalpy (BDE) of 78 kcal/mol .…”

Section: Introductionmentioning

confidence: 99%

Isolable Tin(II) Hydrides Featuring Sterically Undemanding Pincer-Type Ligands and Their Dehydrogenative Sn–Sn Bond Forming Reactions to Distannynes Promoted by Lewis Acidic Tri-sec-butylborane

et al. 2022

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Unlike isolable tin(II) hydrides supported by bulky ligands reported in the literature, this research describes the synthesis and characterization of thermally stable tin(II) hydrides L Ph SnH (1-H) and Me LSnH (2-H) stabilized by sterically undemanding N,N,N-coordinating pincer-type ligands (L Ph = 2,5-dipyridyl-3,4-diphenylpyrrolato; Me L = 2,5-bis(6-methylpyridyl)pyrrolato). The results from previous reports reveal that attempts to access tin(II) hydrides containing less-bulky ligands have had limited success, and decomposition to tin(I) distannynes often occurs. The key to the successful isolation of 1-H and 2-H is the identification of the role of Lewis acidic B s Bu 3 , generated upon delivering hydride from commonly used hydride reagents M[B s Bu 3 H] ("selectrides", M = Li or K). This study details compelling experimental evidence and theoretical results of the role played by B s Bu 3 , which catalyzes the dehydrocoupling reactions of 1-H and 2-H to yield tin(I) distannynes L Ph Sn−SnL Ph (1 2 ) and Me LSn−Sn Me L (2 2 ) with the liberation of H 2 . To avoid the interference of B s Bu 3 , 1-H and 2-H can be isolated in pure forms using pinacolborane as the hydride donor with L Ph SnOMe (1-OMe) and Me LSnOMe (2-OMe) as reactants, respectively. DFT calculations and experimental observations indicate that the coordination of the Sn−H bond of 1-H to B s Bu 3 leaves an electrophilic tin center, rendering the nucleophilic attack by the second equivalent of 1-H forming a Sn−Sn bond.

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Section: Introductionmentioning

confidence: 99%

Isolable Tin(II) Hydrides Featuring Sterically Undemanding Pincer-Type Ligands and Their Dehydrogenative Sn–Sn Bond Forming Reactions to Distannynes Promoted by Lewis Acidic Tri-sec-butylborane

et al. 2022

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“…Compounds of this type can be molecular or polymeric. Molecular derivatives can be regarded as models for polymers and “hybrid” materials based on them [ 12 , 13 , 14 ], including molecular conductors [ 15 ] and semiconductors [ 16 ]. Furthermore, catenated group 14 element derivatives can be used as synthetic reagents.…”

Section: Introductionmentioning

confidence: 99%

Oligoorganogermanes: Interplay between Aryl and Trimethylsilyl Substituents

2022

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Derivatives of main group elements containing element–element bonds are characterized by unique properties due to σ-conjugation, which is an attractive subject for investigation. A novel series of digermanes, Ar3Ge-Ge(SiMe3)3, containing aryl (Ar = p-C6H4Me (1), p-C6H4F (2), C6F5 (3)) and trimethylsilyl substituents, was synthesized by the reaction of germyl potassium salt, [(Me3Si)3GeK*THF], with triarylchlorogermanes, Ar3GeCl. The optical and electronic properties of such substituted oligoorganogermanes were investigated spectroscopically by UV/vis absorption spectroscopy and theoretically by DFT calculations. The molecular structures of compounds 1 and 2 were studied by XRD analysis. Conjugation between all structural fragments (Ge-Ge, Ge-Si, Ge-Ar, where Ar is an electron-donating or withdrawing group) was found to affect the properties.

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“…Still, they remain subjects of considerable interest because, unlike PE, their structures afford electrical conductivity that arises from σdelocalization of electrons. [8][9][10] Furthermore, these electronic properties (in particular band gaps) can be tailored by defining molecule weight, side-group substitution, and/or introducing tensile strain. [10][11][12][13] As such, poly-silanes and germanes exhibit uniquely tunable optical and electrical properties, such as non-linear optical response 14 and photo-induced electron transfer.…”

Section: Introductionmentioning

confidence: 99%

“…Correspondingly, their uses are not as far reaching; polysilanes are primarily employed as lithography resists, − and polygermanes largely remaining as research curiosities. − The limited scope of impact of these materials arises in part because of complications related to their preparation and reactivity. Still, they remain subjects of considerable interest because, unlike PE, their structures afford electrical conductivity that arises from σ-delocalization of electrons. − Furthermore, these electronic properties (in particular band gaps) can be tailored by defining molecular weight, side-group substitution, and/or introducing tensile strain. − As such, polysilanes and germanes exhibit tunable optical and electrical properties, such as nonlinear optical response and photoinduced electron transfer . If a Ge-based PE analogue (i.e., (GeH 2 ) n ) can be prepared, it is reasonable that it will provide additional fundamental insight into polymers made up of catenated noncarbon Group 14 elements (i.e., Si and Ge) and their properties, while offering a platform on which a suite of materials with exquisitely tunable optical and electronic properties can be developed.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Properties, and Derivatization of Poly(dihydrogermane): A Germanium-Based Polyethylene Analogue

Thiessen

et al. 2021

ACS Nano

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Polygermanes are germanium-based analogues of polyolefins and possess polymer backbones made up catenated Ge atoms. In the present contribution we report the preparation of a stable germanium polyethylene analogue -polydihydrogermane (i.e., (GeH2)n) -via two straightforward approaches that involve topotactic deintercalation of the CaGe Zintl phase. The resulting (GeH2)n possess morphologically dependent chemical and electronic properties and thermally decompose to yield amorphous hydrogenated Ge. We also show that the resulting (GeH2)n provide a platform from which functionalized polygermanes can be prepared via thermally-induced hydrogermylation-mediated pendant group substitution. This facile one-step derivatization reaction exploits Ge-H reactivity and opens the door to a wide array of tailored functional polygermanes.

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Catenated Germanium and Tin Oligomers and Polymers

Cited by 12 publications

References 78 publications

Isolable Tin(II) Hydrides Featuring Sterically Undemanding Pincer-Type Ligands and Their Dehydrogenative Sn–Sn Bond Forming Reactions to Distannynes Promoted by Lewis Acidic Tri-sec-butylborane

Isolable Tin(II) Hydrides Featuring Sterically Undemanding Pincer-Type Ligands and Their Dehydrogenative Sn–Sn Bond Forming Reactions to Distannynes Promoted by Lewis Acidic Tri-sec-butylborane

Oligoorganogermanes: Interplay between Aryl and Trimethylsilyl Substituents

Synthesis, Properties, and Derivatization of Poly(dihydrogermane): A Germanium-Based Polyethylene Analogue

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