Higher-Coordinated Molecular Silicon Compounds

Wagler, Jörg; Böhme, Uwe; Kroke, Edwin

doi:10.1007/430_2013_118

Cited by 43 publications

(30 citation statements)

References 357 publications

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“…Fivefold coordinated Si compounds are less common than sixfold derivatives but are also well described. [22] The presence of pyridine in A is proven by IR spectroscopy (Figure S4). Upon heating, pyridine (similar to other Lewis bases) can induce dismutation and the formation of the observed D-and Q-groups.…”

Section: Resultsmentioning

confidence: 99%

[SiS_xH_y]_n – Perhydridopolysilathianes: Cross‐Linked Thio Analogues of Polysiloxanes

et al. 2016

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Polysiloxane‐analogous Si–S compounds have so far not been reported. Transsilylation reactions of the solid pyridine adduct of HSiCl3 with gaseous Me3Si–S–SiMe3 yielded perhydridopolysilathianes. 29Si NMR, FTIR, and Raman spectroscopy; elemental and thermal analysis; XRD; SEM; and gas‐adsorption measurements indicated that the product consists of D‐, T‐, and Q‐units with a composition of ([H2SiS]1.2[HSiS1.5]2.6[SiS2]1.0)n. Formation of the latter is caused by pyridine‐catalyzed dismutation reactions. The polymer is mesoporous with a surface area of 187 m2 g–1; furthermore, it is amorphous and insoluble in organic solvents.

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Section: Resultsmentioning

confidence: 99%

[SiS_xH_y]_n – Perhydridopolysilathianes: Cross‐Linked Thio Analogues of Polysiloxanes

et al. 2016

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“…In addition to d 8 systems, other electron rich TMs may also be capable of forming complexes with TM→Si bonds, as shown by Bourissou et al for the Au(I)→Si system (e.g., XI, Chart 2), in which the d 10 metal is the electron pair donor [34][35][36]. Furthermore, for compounds XII (M = Cu, Ag, Au), The 29 Si NMR shifts (MeSi(pyO) 3 in CDCl 3 : −46.5; Si(pyO) 4 in solid state: −87.9, in CDCl 3 : −97.2) are in support of tetracoordination, as they are similar to (and even more downfield shifted than) the 29 Si NMR shifts of the related phenoxysilanes MeSi(OPh) 3 (−54.0) [31] and Si(OPh) 4 (−101.1) [32], respectively. Some effect of the three-or four-fold capped coordination spheres is evident from the bond angles of the Si atoms, which exhibit notable deviations from the ideal tetrahedral angle (in MeSi(pyO) 3 , O1-Si1-O3 97.39 (5) • and O2-Si1-O3 114.68 (5) • ; in Si(pyO) 4 , two sets of O-Si-O angles of 101.42 (9) • and 113.64(5) • ).…”

Section: Choice Of Metals: Pd(ii) and Cu(i)mentioning

confidence: 93%

“…In the CDCl 3 solution, compound 2 produces one set of broad 1 H NMR signals for the pyO moieties. Thus, this 1 H NMR signal broadening and the less pronounced upfield shift of the 29 Si NMR signal in the solution indicate conformational changes, such as coordination equilibria between isomers MeSi(µ-pyO) 3 CuCl and Me(κO-pyO) 2 Si(µ-pyO)CuCl, the latter with a weaker or absent Si•••Cu interaction. Upon repeated opening/closing of the Schlenk flasks with solutions of 2 in THF or chloroform (e.g., for drawing NMR samples), some blue crystals of the related copper(II) compound 3 formed (Scheme 2) as solvent free crystals (from THF) and chloroform solvate (from the chloroform solution).…”

Section: Reactions Of Mesi(pyo)3 With [Pdcl2(ncme)2] and Cuclmentioning

confidence: 95%

“…The coordination number of tetravalent silicon can easily be enhanced (up to five or six) with the aid of monodentate or chelating ligands [1][2][3][4]. In some of our studies, we have also shown that late transition metals (Ni(II), Pd(II), and Pt(II)) may serve the role of a lone pair donor at hexacoordinate silicon, for example, in I and II (Chart 1) [5][6][7][8].…”

Section: Introductionmentioning

confidence: 99%

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(2-Pyridyloxy)silanes as Ligands in Transition Metal Coordination Chemistry

et al. 2018

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Proceeding our initial studies of compounds with formally dative TM→Si bonds (TM = Ni, Pd, Pt), which feature a paddlewheel arrangement of four (N,S) or (N,N) bridging ligands around the TM–Si axis, the current study shows that the (N,O)-bidentate ligand 2-pyridyloxy (pyO) is also capable of bridging systems with TM→Si bonds (shown for TM = Pd, Cu). Reactions of MeSi(pyO)3 with [PdCl2(NCMe)2] and CuCl afforded the compounds MeSi(µ-pyO)4PdCl (1) and MeSi(µ-pyO)3CuCl (2), respectively. In the latter case, some crystals of the Cu(II) compound MeSi(µ-pyO)4CuCl (3) were obtained as a byproduct. Analogous reactions of Si(pyO)4, in the presence of HpyO, with [PdCl2(NCMe)2] and CuCl2, afforded the compounds [(HpyO)Si(µ-pyO)4PdCl]Cl (4), (HpyO)2Si[(µ-pyO)2PdCl2]2 (5), and (HpyO)2Si[(µ-pyO)2CuCl2]2 (6), respectively. Compounds 1–6 and the starting silanes MeSi(pyO)3 and Si(pyO)4 were characterized by single-crystal X-ray diffraction analyses and, with exception of the paramagnetic compounds 3 and 6, with NMR spectroscopy. Compound 2 features a pentacoordinate Si atom, the Si atoms of the other complexes are hexacoordinate. Whereas compounds 1–4 feature a TM→Si bond each, the Si atoms of compounds 5 and 6 are situated in an O6 coordination sphere, while the TMCl2 groups are coordinated to pyridine moieties in the periphery of the molecule. The TM–Si interatomic distances in compounds 1–4 are close to the sum of the covalent radii (1 and 4) or at least significantly shorter than the sum of the van-der-Waals radii (2 and 3). The latter indicates a noticeably weaker interaction for TM = Cu. For the series 1, 2, and 3, all of which feature the Me–Si motif trans-disposed to the TM→Si bond, the dependence of the TM→Si interaction on the nature of TM (Pd(II), Cu(I), and Cu(II)) was analyzed using quantum chemical calculations, that is, the natural localized molecular orbitals (NLMO) analyses, the non-covalent interaction (NCI) descriptor, Wiberg bond order (WBO), and topological characteristics of the bond critical points using the atoms in molecules (AIM) approach.

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“…The organosilicon complexes such as an organosilatranes have fascinated researchers for a long time due to their different properties and reactivity 10,11 . Among these compounds are substituted propyl chain linked silatranes that constitute a unique class of penta-coordinated silicon compounds [12][13][14] .…”

Section: Introductionmentioning

confidence: 99%

Synthesis, X-Ray Structure and Anti-Bacterial Studies of 1,3-Thiazolylpropylsilatranes

Singh¹,

Promila²,

Saroa³

et al. 2015

Phosphorus, Sulfur, and Silicon and the Related Elements

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Syntheses of 1, 3-thiazolyl functionalized propylsilatranes were carried out by the transesterification reaction of S-(3-triethoxysilylpropyl)mercaptobenzothiazole with triethanolamine, tris(isopropanol)amine and tris(2-aminoethyl)amine. The structures of the synthesized compounds were established by elemental analysis, IR, ( 1 H, 13 C) NMR spectroscopy, mass spectrometry and explored for thermal stability by thermogravimetric analysis. The structure of S-(3-silatranylpropyl)mercaptobenzothiazole was confirmed by single Downloaded by [New York University] at 06:41 01 August 2015 ACCEPTED MANUSCRIPT ACCEPTED MANUSCRIPT 2 crystal X-ray diffraction analysis. All the synthesized silatranes were effectively screened for antibacterial activity against Gram-negative (Escherichia coli and Vibrio cholerae) and Grampositive bacteria (Bacillus subtilis and Staphylococcus aureus).

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Higher-Coordinated Molecular Silicon Compounds

Cited by 43 publications

References 357 publications

[SiS_xH_y]_n – Perhydridopolysilathianes: Cross‐Linked Thio Analogues of Polysiloxanes

[SiS_xH_y]_n – Perhydridopolysilathianes: Cross‐Linked Thio Analogues of Polysiloxanes

(2-Pyridyloxy)silanes as Ligands in Transition Metal Coordination Chemistry

Synthesis, X-Ray Structure and Anti-Bacterial Studies of 1,3-Thiazolylpropylsilatranes

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Higher-Coordinated Molecular Silicon Compounds

Cited by 43 publications

References 357 publications

[SiSxHy]n – Perhydridopolysilathianes: Cross‐Linked Thio Analogues of Polysiloxanes

[SiSxHy]n – Perhydridopolysilathianes: Cross‐Linked Thio Analogues of Polysiloxanes

(2-Pyridyloxy)silanes as Ligands in Transition Metal Coordination Chemistry

Synthesis, X-Ray Structure and Anti-Bacterial Studies of 1,3-Thiazolylpropylsilatranes

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[SiS_xH_y]_n – Perhydridopolysilathianes: Cross‐Linked Thio Analogues of Polysiloxanes

[SiS_xH_y]_n – Perhydridopolysilathianes: Cross‐Linked Thio Analogues of Polysiloxanes