A theoretical study on phosphasilylenes CPSi-X (X=H, CN, NH2 and OMe)

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

doi:10.1016/j.theochem.2005.12.009

Cited by 10 publications

(6 citation statements)

References 46 publications

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“…Following our quest for new carbenonitrenes [25], in this manuscript different multiplicities of (nitrenoethynyl) halomethylenes, X-C-C:C-N, are compared and contrasted at B3LYP, HF, MP2, MP4(SDTQ), CCSD(T), and QCISD(T) levels with 6-311? ?G** basis set, for X = H (1), F (2), Cl (3), and Br (4) (Figs.…”

Section: Resultsmentioning

confidence: 99%

“…However, parallel with many other theoretical reports, we adopt B3LYP6-311? ?G** data for our discussion, since it has emerged quite reliable for computing geometrical parameters due to negligible spin contamination (\S 2 [ = 2.0 for triplet and \S 2 [ = 6.0 for quintet states) (Table S1) which is common for open shell systems [23][24][25][38][39][40]. The relative energies, dipole moments, vibrational zero point energies (ZPE) ( Table 1), geometrical parameters (Fig.…”

Section: Resultsmentioning

confidence: 99%

“…Hence, following our related studies [20][21][22][23][24][25], in this work, we are taking up (nitrenoethynyl)halomethylene, N-C:C-C-X, at theoretical levels (X = H, F, Cl, and Br). In spite of their anticipated instability and experimental inaccessibility, the significance of these species justifies our theoretical scrutiny.…”

Section: Introductionmentioning

confidence: 99%

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Novel quintet and triplet (nitrenoethynyl)halomethylenes at theoretical levels

et al. 2009

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Coupling of a local triplet carbene with a local triplet nitrene through an acetylene linkage gives a new brand of high spin quintet minima (XÀ C ÁÁ ÀC CÀ N ÁÁ ÁÁ ,where X = H, F, Cl, Br), which are rather experimentally unreachable. Placing the same linkage between the local open-shell singlet carbene (r 1 p 1 ) and the local triplet nitrene (p 1 p 1 ) gives triplet minima which are 54-56 kcal/mol more stable than their corresponding quintets. The carbenic angles in both quintets and triplets follow electropositivity of X (H [ Br [ Cl [ F), with every divalent angle in quintet being smaller than the corresponding one in the triplet. Finally no reactive intermediate is observed through connecting singlet states of carbene and nitrene subunits which gives a neutral linear molecule with X-C:C-C:N formula, and show about 70 kcal/mol more stability than the corresponding triplet states. Our results are compared at B3LYP, HF, MP2, MP4(SDTQ), CCSD(T), and QCISD(T) levels using 6-311??G** basis set.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Novel quintet and triplet (nitrenoethynyl)halomethylenes at theoretical levels

et al. 2009

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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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“…In our previous work, we studied silacyclopropenes containing heteroatoms . More recently, we investigated eight silylenic isomers of silapyridine V .…”

Section: Introductionmentioning

confidence: 99%

P‐Heterocyclic silylenes: a survey of stability with density functional theory

Kassaee

Zandi

2011

J of Physical Organic Chem

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The effects of phosphorous atom on the stability, multiplicity, and reactivity of six‐member cyclic silylenes are investigated at B3LYP/AUG‐cc‐pVTZ//B3LYP/6‐31+G* and MP2/6‐311++G**//B3LYP/6‐31+G* coupled with appropriate isodesmic reactions. From a thermodynamic point of view, 1H‐2‐silaphosphinine‐2‐ylidene (1a) and 1H‐4‐silaphosphinine‐4‐ylidene (2a) are relatively the most stable with singlet–triplet energy gaps (ΔES–T) of 37.0 and 28.1 kcal/mol, respectively. The calculated energy barrier for the 1,2‐H shift of 1a to the corresponding 2‐silapyridine (1) is 26.5 kcal/mol, which is lower than the 28.8 kcal/mol required for the 1,4‐H shift of 2a to the corresponding 4‐silapyridine (2). In contrast to the previous reports, isodesmic reactions indicate that π‐donor/σ‐donor phosphorous destabilizes the singlet while stabilizes the triplet state. Both 1a and 2a silylenes appear invulnerable to the head‐to‐head as well as the head‐to‐tail dimerization, inviting experimental explorations. Copyright © 2011 John Wiley & Sons, Ltd.

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A theoretical study on phosphasilylenes CPSi-X (X=H, CN, NH2 and OMe)

Cited by 10 publications

References 46 publications

Novel quintet and triplet (nitrenoethynyl)halomethylenes at theoretical levels

Novel quintet and triplet (nitrenoethynyl)halomethylenes at theoretical levels

In silico quest for stable phosphastannaallenes

P‐Heterocyclic silylenes: a survey of stability with density functional theory

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