Catenated Compounds – Group 14 (Ge, Sn, Pb)

Marschner, Christoph; Hlina, Johann

doi:10.1016/b978-0-08-097774-4.00104-2

Cited by 15 publications

(10 citation statements)

References 378 publications

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“…Previous works by Satge, Castel, Draeger, Mochida, Weinert, Osakada, and Marschner have reported the synthesis and the studies of oligogermane derivatives bearing in general electron-donating groups. To the best of our knowledge, simple germanium compounds containing only electron-withdrawing substituents such as linear oligogermane Cl 3 Ge–GeCl 3 and its higher analogues are almost unknown and highly unstable due to the instability of the Ge–Ge bond in such species and due to the high thermodynamic stability of decomposition products such as GeCl 2 .…”

Section: Introductionmentioning

confidence: 99%

Oligogermanes Containing Only Electron-Withdrawing Substituents: Synthesis and Properties

et al. 2016

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A series of germanes Ar 3 GeX, containing electron-withdrawing substituents [Ar = p-FC 6 H 4 , 1a−d, 1a (X = Cl), 1b (X = Br), 1c (X = H), 1d (X = NMe 2 ); p-F 3 CC 6 H 4 , 2a−d, 2a (X = Cl), 2b (X = Br), 2c (X = H), 2d (X = NMe 2 )], was synthesized and used to prepare symmetrical digermanes Ar 3 Ge−GeAr 3 , (p-FC 6 H 4 ) 3 GeGe(C 6 H 4 F-p) 3 (3), and (p-F 3 CC 6 H 4 ) 3 GeGe(C 6 H 4 CF 3 -p) 3 (4) and trigermane [(p-F 3 CC 6 H 4 ) 3 Ge] 2 Ge(C 6 F 5 ) 2 ( 5) by hydrogermolysis reaction. The properties of all compounds were investigated by multinuclear NMR and for oligogermanes by UV/vis and fluorescence spectroscopy, as well as by electrochemical methods. In addition, the molecular structures of 1a, 1b, 2b, 2c, and 3−5 were studied by X-ray diffraction analysis. Compound 5 showed a significantly shifted UV/visible absorption to the red field in comparison with previously described derivatives.

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Section: Introductionmentioning

confidence: 99%

Oligogermanes Containing Only Electron-Withdrawing Substituents: Synthesis and Properties

et al. 2016

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“…58 For synthetic reasons and owing to better kinetic stabilization, most of the other reported heavier group 13 and 14 congeners exhibit shielding by silyl substituents, such as found in ( t Bu3SiTr)4 (Tr = Al, Ga), ( t Bu3SiTt)4 (Tt = Si, Ge) and (LTr)4 (L = (Me3Si)3C; Tr = In, Tl). [13][14][15][16][17][18][19][20][21]59 However, there are a few special cases: anionic [{(SiMe [{(SiMe3)3C}6Ga8] was obtained under similar conditions, by reaction of GaBr with LiC(SiMe 3 ) 3 at −78°C. However, the molecular structure of the latter shows obvious differences compared to the {Al 7 } motifs, with two tetrahedral {Ga 4 } units being linked through a Ga−Ga bond.…”

Section: Page 5 Of 35 Ccs Chemistrymentioning

confidence: 99%

Cluster Chemistry with ( Pseudo -)Tetrahedra Involving Group 13–15 (Semi-)Metal Atoms

2022

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Compounds containing (pseudo-)tetrahedral main group (semi-)metal units are fundamentally important in three regards. Firstly, they provide us with new strategies for the stabilization of tetrahedral units, such as Pn 4 (Pn = P, As) and their isoelectronic analogs, in the coordination sphere of d-/f-block metal atoms. Secondly, they serve as first-step models for the activation of tetrahedral molecules. Thirdly, they are starting materials for subsequent transformations towards larger clusters or materials. Partial or full isoelectronic replacement of the pnictogen atoms in P 4 or As 4 results in a variety of (pseudo-)tetrahedral anions, Tt 4 4− (Tt = Si, Ge, Sn, Si/Ge), (Ge3Pn) 3− (Pn = P, As; formed in situ), (Tt2Pn2) 2− (Tt/Pn = Ge/P, Ge/As, Sn/Sb, Sn/Bi, Pb/Sb, Pb/Bi), or (TrBi3) 2− (Tr = Ga, In, Tl), and also cations, (P3Ch) + (Ch = S, Se, Te). The anions proved to be excellent starting materials and building blocks for multinary clusters in the context of Zintl chemistry. Such compounds, which push forward the boundary of the intriguing P 4 chemistry, have never been thoroughly summarized before. In this mini review, we introduce all known intact (pseudo-)tetrahedral group 13−15 units, as well as the coordination compounds based on them, along with two new missing links, [Au(η 2 -Tt2Bi2)2] 3− (Tt = Sn, Pb).

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“…Many efforts have been made to develop improved synthetic methods, determine new properties, find relationships between structures and properties, and produce novel materials. Some of the main group element derivatives are molecular compounds of group 14 elements (E = Si [ 5 ], Ge [ 6 ], Sn [ 7 ], Pb [ 8 ]) [ 9 ] containing element–element bonds (oligoorganotetrelanes). Unusual properties (UV/vis absorbance, luminescence, electrochemical activity, thermochromism, etc.)…”

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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Catenated Compounds – Group 14 (Ge, Sn, Pb)

Cited by 15 publications

References 378 publications

Oligogermanes Containing Only Electron-Withdrawing Substituents: Synthesis and Properties

Oligogermanes Containing Only Electron-Withdrawing Substituents: Synthesis and Properties

Cluster Chemistry with ( Pseudo -)Tetrahedra Involving Group 13–15 (Semi-)Metal Atoms

Oligoorganogermanes: Interplay between Aryl and Trimethylsilyl Substituents

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