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

Smallwood, Zoe M.; Davis, Martin F.; Hill, Jimmy; James, Lara J. R.; Portius, Peter

doi:10.1021/acs.inorgchem.9b00150

Cited by 9 publications

(2 citation statements)

References 46 publications

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“…Simultaneously to our publication, Portius and co‐workers reported on a further synthesis strategy for the preparation of [PPN] 2 [Si(CN) 6 ] ([PPN] + = Bis(triphenylphosphine)iminium) as well as on the heavier homologues of germanium and tin ([PPN] 2 [Ge(CN) 6 ] and [PPN] 2 [Sn(CN) 6 ]) …”

Section: Introductionmentioning

confidence: 93%

Hexacyanidosilicates with Functionalized Imidazolium Counterions

et al. 2020

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Functionalized imidazolium cations were combined with the hexacyanidosilicate anion, [Si(CN) 6 ] 2-, by salt metathesis reactions with K 2 [Si(CN) 6 ], yielding novel ionic compounds of the general formula [R-Ph(nBu)Im] 2 [Si(CN) 6 ] {R = 2-Me (1), 4-Me (2), 2,4,6-Me = Mes (3), 2-MeO (4), 2,4-F (5), 4-Br (6); Im = imidazolium}. All synthesized imidazolium hexacyanidosilicates decompose upon thermal treatment above 95°C (96-164°C).

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Section: Introductionmentioning

confidence: 93%

Hexacyanidosilicates with Functionalized Imidazolium Counterions

et al. 2020

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“…Portius et al faced the same problem when synthesizing hexacyanidosilicates as they could show in their publication, which appeared at the same time as ours. [154] Hence, we thought, that utilization of IL-like reaction mixtures could help to solve this problem.…”

Section: Synthesis Of Coordination Polymers Utilizingmentioning

confidence: 99%

Pseudohalogen Chemistry in Ionic Liquids with Non‐innocent Cations and Anions

et al. 2020

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Within the second funding period of the SPP 1708 “Material Synthesis near Room Temperature”,which started in 2017, we were able to synthesize novel anionic species utilizing Ionic Liquids (ILs) both, as reaction media and reactant. ILs, bearing the decomposable and non‐innocent methyl carbonate anion [CO3Me]−, served as starting material and enabled facile access to pseudohalide salts by reaction with Me3Si−X (X=CN, N3, OCN, SCN). Starting with the synthesized Room temperature Ionic Liquid (RT‐IL) [nBu3MeN][B(OMe)3(CN)], we were able to crystallize the double salt [nBu3MeN]2[B(OMe)3(CN)](CN). Furthermore, we studied the reaction of [WCC]SCN and [WCC]CN (WCC=weakly coordinating cation) with their corresponding protic acids HX (X=SCN, CN), which resulted in formation of [H(NCS)2]− and the temperature labile solvate anions [CN(HCN)n]− (n=2, 3). In addition, the highly labile anionic HCN solvates were obtained from [PPN]X ([PPN]=μ‐nitridobis(triphenylphosphonium), X=N3, OCN, SCN and OCP) and HCN. Crystals of [PPN][X(HCN)3] (X=N3, OCN) and [PPN][SCN(HCN)2] were obtained when the crystallization was carried out at low temperatures. Interestingly, reaction of [PPN]OCP with HCN was noticed, which led to the formation of [P(CN)2]−, crystallizing as HCN disolvate [PPN][P(CN⋅HCN)2]. Furthermore, we were able to isolate the novel cyanido(halido) silicate dianions of the type [SiCl0.78(CN)5.22]2− and [SiF(CN)5]2− and the hexa‐substituted [Si(CN)6]2− by temperature controlled halide/cyanide exchange reactions. By facile neutralization reactions with the non‐innocent cation of [Et3HN]2[Si(CN)6] with MOH (M=Li, K), Li2[Si(CN)6] ⋅ 2 H2O and K2[Si(CN)6] were obtained, which form three dimensional coordination polymers. From salt metathesis processes of M2[Si(CN)6] with different imidazolium bromides, we were able to isolate new imidazolium salts and the ionic liquid [BMIm]2[Si(CN)6]. When reacting [Mes(nBu)Im]2[Si(CN)6] with an excess of the strong Lewis acid B(C6F5)3, the voluminous adduct anion {Si[CN⋅B(C6F5)3]6}2− was obtained.

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Synthesis and Characterization of Hypercoordinated Silicon Anions: Catching Intermediates of Lewis Base Catalysis

et al. 2022

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Anionic hypercoordinated silicates with weak donors were proposed as key intermediates in numerous silicon‐based reactions. However, their short‐lived nature rendered even spectroscopic observations highly challenging. Here, we characterize hypercoordinated silicon anions, including the first bromido‐, iodido‐, formato‐, acetato‐, triflato‐ and sulfato‐silicates. This is enabled by a new, donor‐free polymeric form of Lewis superacidic bis(perchlorocatecholato)silane 1. Spectroscopic, structural, and computational insights allow a reassessment of Gutmann's empirical rules for the role of silicon hypercoordination in synthesis and catalysis. The electronic perturbations of 1 exerted on the bound anions indicate pronounced substrate activation.

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

Cited by 9 publications

References 46 publications

Hexacyanidosilicates with Functionalized Imidazolium Counterions

Hexacyanidosilicates with Functionalized Imidazolium Counterions

Pseudohalogen Chemistry in Ionic Liquids with Non‐innocent Cations and Anions

Synthesis and Characterization of Hypercoordinated Silicon Anions: Catching Intermediates of Lewis Base Catalysis

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