From halo-azasilylenes to halo-phosphasilylenes (X-CNSi vs. X-CPSi) at ab initio and DFT levels

Kassaee, M.Z.; Musavi, S.M.; Ghambarian, Mehdi

doi:10.1016/j.jorganchem.2006.01.059

Cited by 7 publications

(1 citation statement)

References 58 publications

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“…In both cases, the deviations of the skeleton from linearity increase from Si to Pb. The singlet-triplet energy separation was estimated for XCPSi [13] and CPSiX [14] systems by ab initio and DFT calculations as a function of electronegativity of the X atom (X = F, Cl, Br, I). The stability of 1,3-diphospha-2-silaallenes -P Si P-relatively to possible isomers was also investigated through theoretical calculations [15].…”

Section: Introductionmentioning

confidence: 99%

In silico quest for stable phosphastannaallenes

Petrar

Bartók

Nemeş

et al. 2012

Comptes Rendus. Chimie

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Section: Introductionmentioning

confidence: 99%

In silico quest for stable phosphastannaallenes

Petrar

Bartók

Nemeş

et al. 2012

Comptes Rendus. Chimie

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A theoretical study of electronic effects in alkyne‐linked reactive intermediates: (nitrenoethynyl)methylenes, (nitrenoethynyl)silylenes, and (nitrenoethynyl)germylenes

Soleimani‐Amiri

Badragheh

Asadbeigi

2019

J Chinese Chemical Soc

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Acetylene‐linked reactive intermediates of (nitrenoethynyl)‐X‐methylenes, (nitrenoethynyl)‐X‐silylenes, and (nitrenoethynyl)‐X‐germylenes are almost experimentally unreachable (X–M–C≡C–N; X=H (1), CN (2), OH (3), NH2 (4), NO2 (5), and CHO (6); M=C, Si, and Ge). The effects of the electron‐donating and electron withdrawing groups were compared and contrasted at seven levels of theory. All singlet species as ground states with one local open‐shell singlet carbene subunit (π1π1) and another local open‐shell singlet nitrene subunit (π1π1) were found to be more stable than their corresponding triplets including one local open‐shell singlet carbene (δ1π1) (or one local closed‐shell singlet carbene [δ2π0]) and another local triplet nitrene subunit (π1π1) with 45.94–77.996 kcal/mol singlet–triplet energy gap (ΔEs‐t). Their relative silylenes and germylenes made reduction of ΔEs‐t, so the triplet ground states were found for species 3 Si, 4 Si, 5 Si, 2 Ge, 3 Ge, 4 Ge, and 5 Ge. All the singlet silylenes/germylenes formed by one local closed‐shell singlet silylenes/germylenes (δ2π0) and one local closed‐shell singlet nitrene subunit (π2π0). Also, one local closed‐shell singlet silylene/germylene subunit (δ2π0) and one local triplet nitrene subunit (π1π1) were observed for triplet silylenes/germylenes. The singlet and triplet species 3 Si, 4 Si, 3 Ge, and 4 Ge, due to their electrophilic (Si4/Ge4) and nucleophilic (X5) centers, could be identified as intermediates in chemical reactions.

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Substituent effects on cyclonona‐3,5,7‐trienylidenes: a quest for stable carbenes at density functional theory level

Koohi

Kassaee

Haerizade

et al. 2015

J of Physical Organic Chem

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Nine boat‐shaped cyclonona‐3,5,7‐trienylidenes are compared and contrasted with respect to their multiplicity, nucleophilicity, electrophilicity, band gap (ΔEHOMO − LUMO), Natural bond orbital (NBO) atomic charge, force constant, as well as the aptitude for dimerization, and rearrangement through proper isodesmic reactions at B3LYP/AUG‐cc‐pVTZ and B3LYP/6‐311++G**//B3LYP/6‐31+G* levels of theory. The nine cyclic carbenes include unsubstituted (1CH2) plus eight α‐cyclopropylcyclonona‐3,5,7‐trienylidenes, which are substituted with ά‐SiMe2, ά‐NMe, ά‐PMe, ά‐O, ά‐S, ά‐CH2, ά‐cyclopropyl, and ά‐CMe2 (2SiMe2, 2NMe, 2PMe, 2O, 2S, 2CH2, 2cyclopropyl, and 2CMe2, respectively). The latter eight species enjoy the stabilizing interaction of the occupied Walsh orbital of cyclopropyl with the vacant pπ orbital of the carbene center (Walshcyclopropyl → pπ carbene). Among them, the singlet closed shell 2NMe appears the most promising for exhibiting the highest relative singlet–triplet energy gap (ΔEs − t = 27.1 kcal mol−1). In contrast, the least stable derivative is triplet 2SiMe2, which exhibits the lowest relative ΔEs − t of −5.5 kcal mol−1. The overall trend of ΔEs‐t is 2NMe > 2PMe > 2S > 2O > 2cyclopropyl > 2CMe2 > 2CH2 > 1CH2 > 2SiMe2. With one negative force constant, the unsubstituted 1CH2 turns out to be a transition state, whereas the rest emerge as minima. Copyright © 2015 John Wiley & Sons, Ltd.

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From halo-azasilylenes to halo-phosphasilylenes (X-CNSi vs. X-CPSi) at ab initio and DFT levels

Cited by 7 publications

References 58 publications

In silico quest for stable phosphastannaallenes

In silico quest for stable phosphastannaallenes

A theoretical study of electronic effects in alkyne‐linked reactive intermediates: (nitrenoethynyl)methylenes, (nitrenoethynyl)silylenes, and (nitrenoethynyl)germylenes

Substituent effects on cyclonona‐3,5,7‐trienylidenes: a quest for stable carbenes at density functional theory level

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