Regioselective Intramolecular Chloride Displacement Leading to Five- or Six-Membered Chelate-Ring Closure and Pentacoordinate Silicon Complexes: A Facile Wawzonek Rearrangement

Yakubovich, S.V.; Gostevskii, B. A.; Kalikhman, I. D.; Kost, Daniel

doi:10.1021/om9002818

Cited by 7 publications

(1 citation statement)

References 28 publications

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“…This goal is achieved through the introduction of a well-known class of reagents, chloromethylsilanes (Scheme ). These reagents have been shown to react with silyl-amides, silyl-hydrazides, and related compounds in two steps: in the first, transsilylation takes place, followed by a molecular rearrangement in which chloride is displaced by an adjacent nitrogen or oxygen nucleophile, with formation of a chelate ring and an increase of the silicon coordination number by one.…”

Section: Introductionmentioning

confidence: 99%

Dinuclear Silicon Complexes of Uracil, Barbituric Acid, and 5,5-Dimethylbarbituric Acid: Hydrolytic Formation of Cyclic Oligomers

et al. 2010

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The synthesis and properties of dinuclear silicon complexes derived from uracil, barbituric acid, and 5,5-dimethylbarbituric acid, through the reaction with (chloromethyl)dimethylchlorosilane and (chloromethyl)dichloro(methyl)silane are described. The oxygen atoms are weakly coordinated to silicon in all three groups of compounds. Mild hydrolysis of the dinuclear compounds leads to formation of cyclic oligomers, with 2-9 monomer units in each, in which the individual units are connected through siloxane groups. Lithium chloride is shown to act as an effective template, restricting oligomerization to dimers and preventing higher-mass product formation.

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Section: Introductionmentioning

confidence: 99%

Dinuclear Silicon Complexes of Uracil, Barbituric Acid, and 5,5-Dimethylbarbituric Acid: Hydrolytic Formation of Cyclic Oligomers

et al. 2010

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Neutral Pentacoordinate Halogeno‐ and Pseudohalogenosilicon(IV) Complexes with an SiSONCX Skeleton (X=F, Cl, Br, I, N, C): Synthesis and Structural Characterization in the Solid State and in Solution

Metz

Theis

Burschka

et al. 2010

Chemistry A European J

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A series of neutral pentacoordinate silicon(IV) complexes with an SiSONCX skeleton (X=F, Cl, Br, I, N, or C) was synthesized and structurally characterized by multinuclear solution-state and solid-state NMR spectroscopy and single-crystal X-ray diffraction. These compounds contain an identical tridentate dianionic S,N,O ligand, a monodentate (pseudo)halogeno ligand (F, Cl, Br, I, NCS, N(3), or CN), and a monodentate organyl ligand (methyl, phenyl, 4-(trifluoromethyl)phenyl, or pentafluorophenyl). For most of these compounds, a dynamic equilibrium between the pentacoordinate silicon(IV) complex and two isomeric tetracoordinate silicon species in solution was observed. Most surprisingly, comparison of two series of analogous compounds containing fluoro, chloro, bromo, or iodo ligands demonstrated that pentacoordination in these series of silicon(IV) complexes is favored in the rank order I approximately Br>Cl>F; i.e., increasing the softness of the halogeno ligand favors pentacoordination.

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Neutral Penta‐ and Hexacoordinate Silicon(IV) Complexes Containing Two Bidentate Ligands Derived from the α‐Amino Acids (S)‐Alanine, (S)‐Phenylalanine, and (S)‐tert‐Leucine

Cota

Beyer

Bertermann

et al. 2010

Chemistry A European J

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The neutral hexacoordinate silicon(IV) complex 6 (SiO(2)N(4) skeleton) and the neutral pentacoordinate silicon(IV) complexes 7-11 (SiO(2)N(2)C skeletons) were synthesized from Si(NCO)(4) and RSi(NCO)(3) (R = Me, Ph), respectively. The compounds were structurally characterized by solid-state NMR spectroscopy (6-11), solution NMR spectroscopy (6 and 10), and single-crystal X-ray diffraction (8 and 11 were studied as the solvates 8 x CH(3)CN and 11 x C(5)H(12) x 0.5 CH(3)CN, respectively). The silicon(IV) complexes 6 (octahedral Si-coordination polyhedron) and 7-11 (trigonal-bipyramidal Si-coordination polyhedra) each contain two bidentate ligands derived from an alpha-amino acid: (S)-alanine, (S)-phenylalanine, or (S)-tert-leucine. The deprotonated amino acids act as monoanionic (6) or as mono- and dianionic ligands (7-11). The experimental investigations were complemented by computational studies of the stereoisomers of 6 and 7.

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Regioselective Intramolecular Chloride Displacement Leading to Five- or Six-Membered Chelate-Ring Closure and Pentacoordinate Silicon Complexes: A Facile Wawzonek Rearrangement

Cited by 7 publications

References 28 publications

Dinuclear Silicon Complexes of Uracil, Barbituric Acid, and 5,5-Dimethylbarbituric Acid: Hydrolytic Formation of Cyclic Oligomers

Dinuclear Silicon Complexes of Uracil, Barbituric Acid, and 5,5-Dimethylbarbituric Acid: Hydrolytic Formation of Cyclic Oligomers

Neutral Pentacoordinate Halogeno‐ and Pseudohalogenosilicon(IV) Complexes with an SiSONCX Skeleton (X=F, Cl, Br, I, N, C): Synthesis and Structural Characterization in the Solid State and in Solution

Neutral Penta‐ and Hexacoordinate Silicon(IV) Complexes Containing Two Bidentate Ligands Derived from the α‐Amino Acids (S)‐Alanine, (S)‐Phenylalanine, and (S)‐tert‐Leucine

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