Hypervalent silicon-containing organosilicon derivatives of nitrogen heterocycles

Воронков, М. Г.; Trofimova, O. M.; Bolgova, Yu. I.; Chernov, N. F.

doi:10.1070/rc2007v076n09abeh003706

Cited by 54 publications

(31 citation statements)

References 15 publications

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“…Synergistic push–pull interactions, such as those defined by three‐center–four‐electron (3c–4e − ) hypercoordination arrangements, have been known for at least 50 years between later Group 14 elements (Si, Ge, Sn, Pb), electron‐rich N, P, O, S donor atoms and axially coordinated electron‐withdrawing substituents (Cl − , Br − , I − ) . X‐ray structural data for several of these Sn species reveals additional donor–ligand coordination to Group 14 elements along with an elongation of the ligand–metal bond trans to the donating group . Hypercoordination to a Sn center is theorized to be the result of a 2e − donation from the formal p‐orbital of the donating ligand into an empty non‐bonding orbital of Sn, which then simultaneously transfers electron density to an antibonding p‐orbital of the electron‐withdrawing substituent .…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Readily Modified Poly(aryl)(alkoxy)stannanes by use of Hypercoordinated Sn Monomers

Pau

D’Amaral

Lough

et al. 2018

Chemistry A European J

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The synthesis and solid‐state molecular structures of two dichlorido(aryl)(alkyl) tin compounds, 5 and 8, both key intermediates to tunable polystannane architectures, are reported. The materials were further investigated by single‐crystal XRD and a DFT analysis of their preferential “open and closed” geometries. Conversion of said compounds to their dihydride analogues was undertaken, followed by their application as monomers for polystannane polymer synthesis. The properties of two asymmetrical polystannanes prepared by transition‐metal‐catalyzed dehydropolymerization of dihydrido(aryl)alkylstannanes (6 and 9) were investigated. The first product was the structurally simple, modest molecular weight, semi‐crystalline light‐ and moisture‐stable polystannane 10 with NMR (119Sn) evidence of prominent Sn←O hypercoordination along the polymer backbone. The second was the lower molecular weight, tosylated four‐coordinate polystannane 11 with no evidence of hypercoordination. Differential scanning calorimetry (DSC) of polymer 10 revealed a reversible semi‐crystalline nature, whereas an amorphous character was detected for polymer 11. Polystannane 10 was also found to be exceptionally stable to both moisture and light (>6 months) and a promising candidate for the design of readily modified (i.e., tunable) polystannane materials.

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Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Readily Modified Poly(aryl)(alkoxy)stannanes by use of Hypercoordinated Sn Monomers

Pau

D’Amaral

Lough

et al. 2018

Chemistry A European J

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“…A distinguishing feature of hypervalent compounds is their stereochemical nonrigidity, which manifests itself as a permutational isomerization around the silicon atom (e.g., ). In other words, the isomerization of this type consists in the intramolecular process of interconversion between isomers, that is, ligand‐site exchange.…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, these processes are conveniently studied by using the dynamic nuclear magnetic resonance (NMR) spectroscopy (an examination of coalescence phenomena and that of the temperature dependence of the line shape). This method is widely applied to determine the free energies of activation for ligand exchange Δ G ≠ …”

Section: Introductionmentioning

confidence: 99%

Ligand‐site exchange in intramolecular complexes of silicon: substituent effects

Кузнецова

Egorochkin

Negrebetsky

et al. 2012

J of Physical Organic Chem

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The intramolecular complexes containing coordination bonds Si←N or Si←O are distinguished for their stereochemical nonrigidity resulting in interconversion between isomers, that is, ligand‐site exchange. The influence of the substituents bound to the silicon atom on the free energies of activation for ligand exchange ΔG≠ of specific interest is poorly understood. In this work, the literature data on substituent influence on the energies ΔG≠ for 13 series of the complexes have been considered, using the correlation analysis. On the basis of the obedience of the energies ΔG≠ to the linear free energy relationship, it has been established for the first time that the ΔG≠ values depend not only on the inductive and resonance effects but also on the polarizability and steric effects of substituents. The reason for the occurrence of the polarizability effect is the appearance of excess charges on Si and N (or O) atoms as a result of intramolecular coordination consisting in the charge transfer from the donor center (N or O atom) to the acceptor one (Si atom). In some series the contribution of the polarizability or steric effect to the overall change in ΔG≠ because of the influence of substituents is a maximum. An understanding of these effects may give a better insight into the mechanism of nucleophilic substitution, involving organoelement compounds. Copyright © 2012 John Wiley & Sons, Ltd.

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“…So far a very few publications have been reported about the synthesis of 1-isothiocyanatosilatrane which involves the direct SieNCS bond [9,10]. A large number of silatranes have been studied due to the reactivity of exocyclic functional groups opposite to the transannular N / Si bond [2,11].…”

Section: Introductionmentioning

confidence: 99%

1-Isothiocyanatosilatrane derived from trisisopropanolamine: Synthesis, characterization, reactivity and theoretical studies

Singh

Saroa

Garg

et al. 2012

Journal of Organometallic Chemistry

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Hypervalent silicon-containing organosilicon derivatives of nitrogen heterocycles

Cited by 54 publications

References 15 publications

Synthesis and Characterization of Readily Modified Poly(aryl)(alkoxy)stannanes by use of Hypercoordinated Sn Monomers

Synthesis and Characterization of Readily Modified Poly(aryl)(alkoxy)stannanes by use of Hypercoordinated Sn Monomers

Ligand‐site exchange in intramolecular complexes of silicon: substituent effects

1-Isothiocyanatosilatrane derived from trisisopropanolamine: Synthesis, characterization, reactivity and theoretical studies

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