Bromo(hydrido)methylbis(4-methylpyridine-<i>N</i>)silicon Bromide at 173K

Hensen, Karl; Kettner, M.; Bolte, Michael

doi:10.1107/s0108270197015801

Cited by 4 publications

(2 citation statements)

References 3 publications

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“…For related complexes with chelating bidentate N-donor ligands, the formation of complexes of type D was observed (e.g., [SiCl2(bipy)2] 2+ [28], [Si(OH)2(bipy)2] 2+ [29], [Si(OMe)2(phen)2] 2+ [30]). In addition to these classes A, B, C, and D of pyridine-Si complexes, other coordination motifs have also been encountered, such as the mono-cationic pentacoordinate Si complex [SiHMeBr(4-methylpyridine)2] + [31], and other pyridine derivatives have been engaged in silicon coordination chemistry as well, e.g., terpyridines [32].…”

Section: Introductionmentioning

confidence: 99%

“…The latter were obtained via (3+2)-cycloaddition reactions of nitriles and Si-bound azido groups. In addition to these classes A, B, C, and D of pyridine-Si complexes, other coordination motifs have also been encountered, such as the mono-cationic pentacoordinate Si complex [SiHMeBr(4-methylpyridine) 2 ] + [31], and other pyridine derivatives have been engaged in silicon coordination chemistry as well, e.g., terpyridines [32].…”

Section: Introductionmentioning

confidence: 99%

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The Hexacoordinate Si Complex SiCl4(4-Azidopyridine)2—Crystallographic Characterization of Two Conformers and Probing the Influence of SiCl4-Complexation on a Click Reaction with Phenylacetylene

Riedel,

Gerwig,

Gerlach

et al. 2023

Inorganics

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4-Azidopyridine (1) and SiCl4 react with the formation of the hexacoordinate silicon complex SiCl4(4-azidopyridine)2 (2). Upon dissolving in warm chloroform, the complex dissociates into the constituents 1 and SiCl4 and forms back upon cooling. Depending on the cooling, two different crystalline modifications of 2 were obtained, which feature two different trans-conformers. Slow cooling to room temperature afforded conformer 2′, which features coplanar pyridine rings. Rapid cooling to −39 °C afforded crystals of conformer 2″, in which the planes of the pyridine ligands are nearly orthogonal to one another. Whereas 2′ resembles the molecular arrangement of various other known SiX4(pyridine)2 (X = halide) complexes, 2″ represents the first crystallographically confirmed example of a SiX4(pyridine)2 complex in this conformation. Conformers 2′ and 2″ were studied with 13C and 29Si solid state NMR spectroscopy. Their differences in 29Si chemical shift anisotropy, as well as energetic differences, were further investigated with computational analyses. In spite of the similar stabilities of the two conformers as isolated molecules, the crystal packing of 2″ is less stable, and its crystallization is interpreted as a kinetically controlled effect of seed formation. (3+2)-cycloaddition of 1 and phenylacetylene in toluene at 110 °C yields a mixture of 1-(4-pyridyl)-4-phenyl-1,2,3-triazole (1,4-3) and 1-(4-pyridyl)-5-phenyl-1,2,3-triazole (1,5-3) in approximate 1:2 molar ratio. The crystal structures of the two isomers were determined via X-ray diffraction. In chloroform (at 60 °C), this reaction is slow (less than 2% conversion within 4 h), but the presence of SiCl4 enhanced the rate of the reaction slightly, and it shifted the triazole isomer ratio to ca. 1:6 in favor of 1,5-3.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The Hexacoordinate Si Complex SiCl4(4-Azidopyridine)2—Crystallographic Characterization of Two Conformers and Probing the Influence of SiCl4-Complexation on a Click Reaction with Phenylacetylene

Riedel,

Gerwig,

Gerlach

et al. 2023

Inorganics

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Disilicon Complexes with Two Hexacoordinate Si Atoms: Paddlewheel‐Shaped Isomers with (ClN₄)SiSi(S₄Cl) and (ClN₂S₂)SiSi(S₂N₂Cl) Skeletons

Wagler¹,

Brendler²,

Heine³

et al. 2013

Chemistry A European J

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The reaction of 1-methyl-3-trimethylsilylimidazoline-2-thione with hexachlorodisilane proceeds toward substitution of four of the disilane Cl atoms during the formation of disilicon complexes with two neighboring hexacoordinate Si atoms. The N,S-bidentate methimazolide moieties adopt a buttressing role, thus forming paddlewheel-shaped complexes of the type ClSi(μ-mt)4 SiCl (mt=methimazolyl). Most interestingly, three isomers (i.e., with (ClN4 )SiSi(S4 Cl), (ClN3 S)SiSi(S3 NCl), and (ClN2 S2 )SiSi(S2 N2 Cl) skeletons as so-called (4,0), (3,1), and cis-(2,2) paddlewheels) were detected in solution by using (29) Si NMR spectroscopic analysis. Two of these isomers could be isolated as crystalline solids, thus allowing their molecular structures to be analyzed by using X-ray diffraction studies. In accord with time-dependent NMR spectroscopy, computational analyses proved the cis-(2,2) isomer with a (ClN2 S2 )SiSi(S2 N2 Cl) skeleton to be the most stable. The compounds presented herein are the first examples of crystallographically evidenced disilicon complexes with two SiSi-bonded octahedrally coordinated Si atoms and representatives of the still scarcely explored class of Si coordination compounds with sulfur donor atoms.

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Pentacoordinate Silicon Complexes with N‐(2‐pyridylmethyl)salicylamide as a Dianionic (ONN′) Tridentate Chelator

Schwarz

Brendler

Kroke

et al. 2012

Zeitschrift anorg allge chemie

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The title compound, N-(2-pyridylmethyl)salicylamide (1), was synthesized by ester aminolysis of methyl salicylate and 2-picolylamine. In the presence of triethylamine as a supporting base, the salicylamide moiety reacts with the organodichlorosilanes RRЈSiCl 2 to form the desired six-membered heterocycles of the type RRЈSi-O-(o-C 6 H 4 )-C(=O)N(pic), with pic being the 2-pyridylmethyl (i.e., 2-picolyl) moiety and RRЈ = Me,Me (2a); Me,Ph (2b); Ph,Ph (2c); Bn,Bn (2d); All,Ph (2e) and Ph,H (2f). Despite the absence of notable ring strain release Lewis acidity (i.e., only a six-membered chelate is 1768 formed by the dianion, and smaller rings are not present in the compound), the poor electron withdrawal from silicon by its C-or Hsubstituents and the flexible methylene bridge between the salicylamide and the pyridine moiety, the pyridine N donor atom furnishes pentacoordinate silicon coordination spheres in all of these compounds 2a-2f. The coordination number of the silicon atom was confirmed by single-crystal X-ray diffraction analysis for the solid state and by 29 Si NMR spectroscopy for the solution state. Scheme 1. Examples of neutral and cationic halosilane pyridine adducts with hexa-or pentacoordinate silicon atom.

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Bromo(hydrido)methylbis(4-methylpyridine-N)silicon Bromide at 173K

Cited by 4 publications

References 3 publications

The Hexacoordinate Si Complex SiCl4(4-Azidopyridine)2—Crystallographic Characterization of Two Conformers and Probing the Influence of SiCl4-Complexation on a Click Reaction with Phenylacetylene

The Hexacoordinate Si Complex SiCl4(4-Azidopyridine)2—Crystallographic Characterization of Two Conformers and Probing the Influence of SiCl4-Complexation on a Click Reaction with Phenylacetylene

Disilicon Complexes with Two Hexacoordinate Si Atoms: Paddlewheel‐Shaped Isomers with (ClN₄)SiSi(S₄Cl) and (ClN₂S₂)SiSi(S₂N₂Cl) Skeletons

Pentacoordinate Silicon Complexes with N‐(2‐pyridylmethyl)salicylamide as a Dianionic (ONN′) Tridentate Chelator

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Bromo(hydrido)methylbis(4-methylpyridine-N)silicon Bromide at 173K

Cited by 4 publications

References 3 publications

The Hexacoordinate Si Complex SiCl4(4-Azidopyridine)2—Crystallographic Characterization of Two Conformers and Probing the Influence of SiCl4-Complexation on a Click Reaction with Phenylacetylene

The Hexacoordinate Si Complex SiCl4(4-Azidopyridine)2—Crystallographic Characterization of Two Conformers and Probing the Influence of SiCl4-Complexation on a Click Reaction with Phenylacetylene

Disilicon Complexes with Two Hexacoordinate Si Atoms: Paddlewheel‐Shaped Isomers with (ClN4)SiSi(S4Cl) and (ClN2S2)SiSi(S2N2Cl) Skeletons

Pentacoordinate Silicon Complexes with N‐(2‐pyridylmethyl)­salicylamide as a Dianionic (ONN′) Tridentate Chelator

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Disilicon Complexes with Two Hexacoordinate Si Atoms: Paddlewheel‐Shaped Isomers with (ClN₄)SiSi(S₄Cl) and (ClN₂S₂)SiSi(S₂N₂Cl) Skeletons

Pentacoordinate Silicon Complexes with N‐(2‐pyridylmethyl)salicylamide as a Dianionic (ONN′) Tridentate Chelator