The New λ6Si‐Silicate Dianion [Si(NCO)6]2−: Synthesis and Structural Characterization of [K(18‐crown‐6)]2[Si(NCO)6]

Seiler, Oliver; Burschka, Christian; Götz, Kathrin; Kaupp, Martin; Metz, Stefan; Tacke, Reinhold

doi:10.1002/zaac.200700189

Cited by 17 publications

(6 citation statements)

References 40 publications

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“…2.743 A ˚), which in turn is masked by crown ether. 9 A comparison of the [Si(NCO) 6 ] 2ion in crystalline 1a and the previously reported structure reveals that the bond lengths are in good agreement, however, the Si-N-C angles are significantly more obtuse in 1a. This feature is ascribed to a more extended 4).…”

Section: Resultssupporting

confidence: 52%

A new hexakis(isocyanato)silicate(IV) and the first neutral Lewis-base adducts of silicon tetraisocyanate

Portius

Davis

2010

Dalton Trans.

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The new silicates K2Si(NCE)6, E = O, S (1a,b) were synthesised directly by reaction of silicon tetrachloride with potassium cyanate or thiocyanate. 1a,b can be converted to the salts (PPN)2[Si(NCE)6] (2a,b) with bulky cations (PPN+ = N(PPh3)2+), which contain isolated silicate dianions. Reaction of 1a with diimines affords the hexacoordinate complexes Si(NCO)4L, L = bpy (3), phen (4), which are the first isolated neutral adducts to Si(NCO)4. The compounds were characterised by a combination of IR and NMR spectroscopies, MS, TGA, DSC and X-ray diffraction.

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Section: Resultssupporting

confidence: 52%

A new hexakis(isocyanato)silicate(IV) and the first neutral Lewis-base adducts of silicon tetraisocyanate

Portius

Davis

2010

Dalton Trans.

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“…[Me 3 SiF(CN)] − ‐Ionen wurden als starke nukleophile Cyanidquelle für S N 2‐Reaktionen diskutiert, während [Me 3 Si(CN) 2 ] − und [Me 3 Si(CN)Cl] − als reaktive Spezies in enantioselektiven Cyanosilylierungen von Aldehyden und Ketonen beschrieben wurden . Erstaunlicherweise sind keine Salze mit dem Hexacyanidosilikatdianion [Si(CN) 6 ] 2− bekannt, während die analogen Hexapseudohalogenidosilikate des Azids, (Iso‐)Cyanats und Thiocyanats isoliert wurden. Darüber hinaus haben Fehlhammer et al.…”

Section: Figureunclassified

Cyanidosilikate – Synthese und Struktur

et al. 2019

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Ausgehend von Fluoridosilikat-Vorstufen in reinem Cyantrimethylsilan, Me 3 Si-CN,w urde eine Reihe verschiedener Ammoniumsalze[ R 3 NMe] + (R = Et, n Pr, n Bu) mit den neuen [SiF(CN) 5 ] 2À -und [Si(CN) 6 ] 2À -Dianionen in einfachen, temperaturgesteuerten F À /CN À -Austauschreaktionen synthetisiert. Mit zersetzbaren, nicht-unschuldigen Kationen wie [R 3 NH] + konnten Metallsalzed es Typs M 2 [Si(CN) 6 ]( M + = Li + ,K + )d urchN eutralisationsreaktionen mit entsprechenden Metallhydroxiden hergestellt werden. Die ionische Flüssigkeit [BMIm] 2 [Si(CN) 6 ]( Schmp. = 72 8 8C) wurde durch eine Salzmetathesereaktion erhalten. Alle synthetisierten Salzekonnten in guten Ausbeuten isoliert und vollständig charakterisiert werden.

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“…Pseudohalogen complexes of the type EY n q – are isolable for most p -block elements in groups 13–15: Y = N 3 (B–Tl, Si–Sn, P–Bi), NCS (P, Si–Sn), NCO (Si, Ge, Sn), NO 3 (B, Al, Si–Sn). In group 14, they take the form of EL 4 and EL 6 2– (E = Si–Pb, L = N 3 , NO 3 , NCO, NCS, NCSe). − However, there are only very few homoleptic cyanido complexes. This group of complexes is restricted to coordination centers of the less electronegative elements in groups 13 and 15 as P(CN) 3 , Ga(CN) 4 – , E(CN) 5 2– (E = In, Tl, Sb, Bi) and Bi(CN) 6 3– . − In group 14, the set of known complexes consist of the E(CN) 4 type (E = Ge, Sn), for which, apart from in situ 119 Sn NMR spectral data for the Cl/CN ligand exchange to form Sn(CN) 6 2– , little analytical data is available. − CN ligands possess a comparably low oxidation potential and this effects, for instance, the low thermal stability of P(CN) 5 which readily eliminates cyanogen at ambient temperature to form P(CN) 3 .…”

Section: Introductionmentioning

confidence: 99%

Syntheses, Structures, and Infrared Spectra of the Hexa(cyanido) Complexes of Silicon, Germanium, and Tin

et al. 2019

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The rare octahedral EC6 coordination skeleton type is unknown for complexes with coordination centers consisting of Group 14 elements. Here, the first examples of such EC6 species, the hexacoordinate homoleptic cyanido complexes E(CN)6 2− , E = Si, Ge, Sn, have been synthesized from element halides SiCl4, GeCl4 and SnF4 and isolated as salts with PPN counter ions (PPN + = (Ph3P)2N + ) on a scale 0.2-1 g. Characterization by spectroscopic techniques and by structure determination through single crystal crystallographic methods show that these pseudohalogen complexes have effective octahedral symmetry in solution and in the solid state.Infrared spectra obtained in solution reveal that the T1u symmetric IR-active vibrations in all three complexes have unusually small oscillator strengths. The observed reluctance of Si(CN)6 2− , Ge(CN)6 2− and Sn(CN)6 2− to form from chloro-precursors was rationalized in terms of Gibbs free energies, which were found by ab initio calculations at the CCSD(T)-F12b/aug-cc-pVTZ(-PP)-F12 level of theory to be small or even positive. The work demonstrates that E(CN)6 2− complexes of silicon, germanium and tin are in fact stable at r.t. and exist as well-defined units in the presence of non-coordinating counter-ions. The results add to our understanding of the chemistry of pseudohalogens and structure and bonding.

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The New λ⁶Si‐Silicate Dianion [Si(NCO)₆]²⁻: Synthesis and Structural Characterization of [K(18‐crown‐6)]₂[Si(NCO)₆]

Cited by 17 publications

References 40 publications

A new hexakis(isocyanato)silicate(IV) and the first neutral Lewis-base adducts of silicon tetraisocyanate

A new hexakis(isocyanato)silicate(IV) and the first neutral Lewis-base adducts of silicon tetraisocyanate

Cyanidosilikate – Synthese und Struktur

Syntheses, Structures, and Infrared Spectra of the Hexa(cyanido) Complexes of Silicon, Germanium, and Tin

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