Hyperbonding and Hypercoordination in Main-Group Chemistry

Minyaev, R. M.; Gribanova, T. N.

doi:10.1016/b978-0-08-097774-4.00904-9

Cited by 10 publications

(4 citation statements)

References 170 publications

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“…The 3c-4ebond is a concept used to describe hypervalent compounds which exceed the standard octet of valence electrons. [19][20][21] In a tin (IV) compound containing a ligand capable of hypercoordination, trigonal bipyramidal geometries are preferred where the 3c-4ebonds are typically observed in the axial position (Figure 4). 20 The lone pair of electrons on Y are donated into the non-bonded molecular orbitals of the tin.…”

Section: C-4e -Bond Conceptmentioning

confidence: 99%

Hypercoordinated oxazoline and ethyl pyridyl organotin compounds: potential routes to stable polystannanes

Bender

2021

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Tetraorganotin chelating tin (IV) compounds containing a rigid (10) and a semi-flexible (18) oxazoline ligand were synthesized by a reaction between the lithiated oxazoline and Ph3SnCl in good yields. Conversion into their corresponding dihalide species by reaction with two equivalents of bromine was undertaken to yield the dibromide species, 13 and 20 respectively. X-ray crystallography of these compounds revealed relatively short tin-nitrogen bond distances (10:2.762 13: 2.383, 18: 3.234 Å). These all fall within the Van der Waal radii of a tin-nitrogen bond and all adopt a distorted trigonal bipyramidal geometry in the solid state. Compounds 13 and 20 were converted into the corresponding dihydrides by reaction with NaBH4. Polymerization of the corresponding tin dihydrides produced low molecular weight polymers, 10,100 Da for the rigid species (16) and 3,200 Da for the semi-flexible tin species (22). A tetraorganotin compound containing a chelating ethyl pyridyl ligand (23) was synthesized by reacting 2-vinyl pyridine with triphenyltin hydride via a hydrostannylation reaction which was further reacted with two equivalents of bromine to yield the dibromide species (24). The X-ray crystallographic data of 23 and 24 showed relatively short Sn-N bond lengths of 2.888(2) Å and 2.363(5) Å respectively. Compound 24 will be investigated in the future for the stabilization of polystannanes following the synthesis of the dihydride species.

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Section: C-4e -Bond Conceptmentioning

confidence: 99%

Hypercoordinated oxazoline and ethyl pyridyl organotin compounds: potential routes to stable polystannanes

Bender

2021

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“…The chemistry of organosilicon hypervalent compounds was intensively developed over last several decades. The methods of synthesis were designed and the data on the structure and reactivity were obtained for organosilicon compounds with intramolecular coordination bond D → Si (D = O, N), which led to their use as synthons and catalysts in synthetic and medicinal chemistry as well as in the chemistry of materials. − The nature of hypervalent D → Si bonding has also been explored. ,− However, some problems still remain to be solved. Thus, for (O–Si)-monochelate N -[(halogeno)silylmethyl]carboxamides and their analogues, which are classical representatives of pentacoordinate organosilicon compounds, the synthetic approach, structure, and reactivity are well known ,− but still there is no clear understanding of the process of formation of these structures, which would allow us to direct the reaction toward the selective formation of the desired products.…”

Section: Introductionmentioning

confidence: 99%

Tetrel Bonding along the Pathways of Transsilylation and Alkylation ofN-Trimethylsilyl-N-methylacetamide with Bifunctional (Chloromethyl)fluorosilanes

et al. 2019

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A quantum chemical study has been carried out on the complexes formed in the first stage of the reaction of (chloromethyl)trifluorosilane with an ambident nucleophile, N-trimethylsilyl-N-methylacetamide, existing in the amide and imidate tautomeric forms. The analysis of molecular electrostatic potential maps of the electrophile molecule revealed the presence of two σ-holes belonging to the Si and C atoms. Each of the two tautomers of the nucleophile form complexes having O···Si, O···C, N···Si, and N···C bonds of different characters. The natural bond orbital and quantum theory of atoms in molecules analyses showed the presence of the O···Si and O···C tetrel bonds or of electrostatic interaction in the complexes with the amide tautomer, depending on the orientation of the components. The imidate tautomer forms a complex with covalent N–Si bond, whereas the N···C bond is very weak. The effect of silicon atom arrangement on the structure of complexes between N-trimethylsilyl-N-methylacetamide and bifunctional silanes ClCH2SiX n F3–n (X = Me, OMe, Cl, n = 1, 2) and the effect of σ-hole tetrel bonding interactions on the reaction pathways are discussed.

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“…x List of Tables Table 1: MP2/LanL2DZ calculated M-O distances of various acrolein derivatives. 3 ................... 119 Sn data of organotin compounds prepared by the Holecek Group 8a-f and the Ruzicka Group. 9 Solvents used were CDCl3 (*), Tol-d8 ( †), CH2Cl2 ( ‡), and C6D6 ( §).…”

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confidence: 99%

“…2 These species can exceed the number of valence electrons dictated by the octet rule though an inter-or intra-molecular interaction from an electron-abundant atom (or donor atom, D) to a main group atom (M). 3 This forms a hypercoordinate or 3-center-4-electron bond, defined as a delocalization of bonding electrons along 3 atoms that lie in the same plane. This bond is characterized by the N-M-L notation, of which denotes the number of electrons associated with M (N), the main heteroatom, M, and the number of bound ligands to that heteroatom (L).…”

mentioning

confidence: 99%

Hypercoordinated Organotin(IV) Compounds Containing ĸ²-C,O- And ĸ²,N- Chelating Ligands: Synthesis, Characterization, and Polymerization Behaviour

Loungxay¹

2021

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Rigid homopolystannanes and alternating polystannanes containing a benzyl methoxy ether (C,O) or benzyl dimethyl amine (C,N) ligand were prepared using either a direct approach, lithiation and transmetallation, or an alternative approach, either sequential chlorinations or brominations. X-ray crystallographic studies of 41 and 45 were conducted to find 41 in a distorted tetrahedral geometry with moderate hypercoordinate interaction (Sn-N: 2.917 Å) while 45 in a distorted trigonal bipyramidal with strong hypercoordinate interaction (Sn-N: 2.403 Å). Hydrogenation of 31 and 33 produced 42 and 43 in moderate-to-good yields. Dehydrocoupling polymerization produced modest molecular weight, rigid C,O- (Mw = 3.03 × 10⁴ Da, PDI: 1.4) and C,N- (Mw = 3.10 × 10⁴ Da, PDI: 1.82) homopolymers 56 and 57. Finally, condensation polymerization was attempted to produce low molecular weight (Mw = 1.30 × 10⁴ Da, PDI: 2.0) C,O- alternating polymer 60 and oligomer 61 (Mw = 0.92 × 10⁴ Da, PDI: 2.71).

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Hyperbonding and Hypercoordination in Main-Group Chemistry

Cited by 10 publications

References 170 publications

Hypercoordinated oxazoline and ethyl pyridyl organotin compounds: potential routes to stable polystannanes

Hypercoordinated oxazoline and ethyl pyridyl organotin compounds: potential routes to stable polystannanes

Tetrel Bonding along the Pathways of Transsilylation and Alkylation ofN-Trimethylsilyl-N-methylacetamide with Bifunctional (Chloromethyl)fluorosilanes

Hypercoordinated Organotin(IV) Compounds Containing ĸ²-C,O- And ĸ²,N- Chelating Ligands: Synthesis, Characterization, and Polymerization Behaviour

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