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Воронков, М. Г.; Boyarkina, E. V.; Gavrilova, G. M.; Basenko, S. V.

doi:10.1023/a:1014271706096

Cited by 5 publications

(4 citation statements)

References 2 publications

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“…Reaction of ( p -tolyl)SiCl 3 with 2 equiv of Me 3 Si(OPO) and 1 equiv of Me 3 SiI or Me 3 SiOSO 2 CF 3 afforded complexes 7 and 8 , respectively, in quantitative yields (eq ). , In DMSO- d 6 , both 7 and 8 exhibited 1 H, 13 C, and 29 Si NMR spectra identical with those of 2 , and therefore, this strongly supports that all three complexes exist as separated ion pairs in solution. The connectivity of 8 (Figure ) was established by X-ray diffraction analysis, which revealed an SP geometry with trans -OPO ligands and a weakly interacting triflate ion in a regular position off of the vacant coordination site, with the shortest Si···OSO 2 CF 3 distance of 3.237(2) Å.…”

Section: Synthesissupporting

confidence: 58%

Neutral and Cationic Bis-Chelate Monoorganosilicon(IV) Complexes of 1-Hydroxy-2-pyridinone

Koch¹,

Brennessel

Kraft

2017

Organometallics

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A series of spirocyclic monoorganosilicon compounds of the form RSi(OPO) 2 Cl [R = phenyl (1 1); p-tolyl (2 2); benzyl (3 3); Me (4 4); t Bu (5 5); thexyl (6 6)] (OPO = 1-oxo-2-pyridinone) was synthesized and characterized by 1 H , 13 C, and 29 Si NMR spectroscopy, X-ray crystallography, and elemental analysis. In the solid state, complexes 1 1, 2 2, and 3 3 are neutral and possess cis-OPO ligands in an octahedral arrangement, and complexes 4 4, 5 5, and 6 6 are cationic and possess effectively trans-OPO ligands in nearly ideal square pyramidal geometries along the Berry-pseudorotation coordinate. In 4-6 4-6, chloride dissociation is attributed to the additive effect of multiple intermolecular C-H•••Cl interactions in their crystals. In DMSO-d 6 solution, compounds 1 1-6 6 form cationic hexacoordinate DMSO adducts with trans-OPO ligands, all of which undergo dynamic isomerization with energy barriers of ~18-19 kcal/mol. Compounds with better leaving groups, (p-tolyl)Si(OPO) 2 X [X = I (7 7); X = triflate (8 8)], exhibit identical solution NMR spectra as 2 2, supporting anion dissociation in each. The fluoride derivatives RSi(OPO) 2 F [R = benzyl (9 9); Me (10 10)] exhibit hexacoordinate geometries with cis-OPO ligands in the solid state and exhibit dynamic isomerization in solution. Overall, these studies indicate, in both the solid and solution states, that the trans-OPO ligand arrangement is favored when anions are dissociated and a cis-OPO ligand arrangement when anions are coordinated.

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Section: Synthesissupporting

confidence: 58%

Neutral and Cationic Bis-Chelate Monoorganosilicon(IV) Complexes of 1-Hydroxy-2-pyridinone

Koch¹,

Brennessel

Kraft

2017

Organometallics

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“…318,[326][327][328][329] The [SiF 4 (dmf) 2 ] is formed in the curious reaction of RSiF 3 with dmf. 330 322 In contrast, the arsine oxides OAsR 3 (R = Me or Ph) do not give simple adducts with SiF 4 , but instead form [R 3 AsOH] + cations, isolated as fluorosilicate salts. 322 Complexes of SiF 4 with neutral N-donor ligands are rather rare, but generally more robust than the O-donor complexes described above.…”

Section: Siliconmentioning

confidence: 99%

Medium and high oxidation state metal/non-metal fluoride and oxide–fluoride complexes with neutral donor ligands

2013

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While most high and medium oxidation state (O.S. ≥ 3) metal and non-metal fluorides and oxide fluorides are strong Lewis acids, exploration of their coordination chemistry with neutral ligands has been limited and mostly non-systematic. This is despite the very different properties conferred on the acceptor centre by the small electronegative fluoride ligands compared to the heavier halides. This article sets out these key differences, discusses possible synthetic routes, the key characterisation techniques, and appropriate bonding models. Current knowledge of the coordination chemistry of d, f and p-block fluorides and oxide fluorides with neutral ligands (with donor atoms drawn from Groups 15 and 16 and including N-heterocyclic carbenes) is then presented and discussed, and the differences in properties compared to complexes containing the heavier halides are illustrated. The emphasis is on work published post 1990, but earlier work is also included as essential background and where no more recent information exists. Attention is drawn to unexplored areas meriting investigation and to possible applications of these complexes.

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“…33 Aqueous HF also converts Ph 3 AsO to Ph 3 AsF 2 . 34 The complexes [SiF 4 (pyNO) 2 ] and [SiF 4 (dmso) 2 ] have been described several times, 19b,19c, 35 but with limited data. Both are readily isolated as hygroscopic white crystalline solids by reaction This journal is © The Royal Society of Chemistry 2011 of SiF 4 with the ligands in CH 2 Cl 2 or toluene solution.…”

Section: O-mentioning

confidence: 99%

Hypervalent neutral O-donor ligand complexes of silicon tetrafluoride, comparisons with other group 14 tetrafluorides and a search for soft donor ligand complexes

et al. 2011

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The hypervalent adducts of SiF(4), trans-[SiF(4)(R(3)PO)(2)] (R = Me, Et or Ph), cis-[SiF(4){R(2)P(O)CH(2)P(O)R(2)}] (R = Me or Ph), cis-[SiF(4)(pyNO)(2)] and trans-[SiF(4)(DMSO)(2)] have been prepared from SiF(4) and the ligands in anhydrous CH(2)Cl(2), and characterised by microanalysis, IR and VT multinuclear ((1)H, (19)F, (31)P) NMR spectroscopy. The NMR studies show extensive dissociation at ambient temperatures in non-coordinating solvents, but mixtures of cis and trans isomers of the monodentate ligand complexes were identified at low temperatures. Crystal structures are reported for trans-[SiF(4)(R(3)PO)(2)] (R = Me or Ph), and cis-[SiF(4)(pyNO)(2)]. The GeF(4) analogues cis-[GeF(4){R(2)P(O)(CH(2))(n)P(O)R(2)}] (R = Me or Ph, n = 1; R = Ph, n = 2) were similarly characterised and the structures of cis-[GeF(4){R(2)P(O)CH(2)P(O)R(2)}] (R = Me or Ph) determined. The reaction of R(3)AsO (R = Me or Ph) with SiF(4) does not give simple adducts, but forms [R(3)AsOH](+) cations as fluorosilicate salts. SiF(4) adducts of some ether ligands (including THF, 12-crown-4) were also characterised by (19)F NMR spectroscopy in solution at low temperatures (∼190 K), but are fully dissociated at room temperature. Attempts to isolate, or even to identify, SiF(4) adducts with phosphine or thioether ligands in solution at 190 K were unsuccessful, contrasting with the recent isolation and detailed characterisation of GeF(4) analogues. The chemistry of SiF(4) with these oxygen donor ligands, and with soft donors (P, As, S or Se), is compared and contrasted with those of GeF(4), SnF(4) and SiCl(4). The key energy factors determining stability of these complexes are discussed.

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Cited by 5 publications

References 2 publications

Neutral and Cationic Bis-Chelate Monoorganosilicon(IV) Complexes of 1-Hydroxy-2-pyridinone

Neutral and Cationic Bis-Chelate Monoorganosilicon(IV) Complexes of 1-Hydroxy-2-pyridinone

Medium and high oxidation state metal/non-metal fluoride and oxide–fluoride complexes with neutral donor ligands

Hypervalent neutral O-donor ligand complexes of silicon tetrafluoride, comparisons with other group 14 tetrafluorides and a search for soft donor ligand complexes

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