64. The microwave spectrum, structure, and dipole moment of nitryl chloride

Millen, D. J.; Sinnott, K. M.

doi:10.1039/jr9580000350

Cited by 35 publications

(7 citation statements)

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“…Second, the distance r(N´´´Cl) 2.090 , determined by isotopic substitution at both N and Cl, is short compared with the value of 2.639(3) in the weakly bound (k s 12.3 N m À1 ) HCN´´´ClF. [56] In fact, r(N´´´Cl) in (CH 3 ) 3 N´´´ClF is closer to the covalent distances r(NÀCl) 1.84 and 1.754 (2) in O 2 NCl [170] and NCl 3 , [171] respectively. Third, c zz (Cl) in (CH 3 ) 3 N´´´ClF can be interpreted in terms of about a 60 % contribution of the form [(CH 3 ) 3 NCl] ´´´FÀ by using arguments based on comparisons with values of c zz (Cl) along the Cl bond direction z in molecules such as CH 3 OCl, as discussed in detail in reference [169].…”

Section: The Halogen Bond B´´´xy and How To Encourage Charge Transfermentioning

confidence: 93%

Prereactive Complexes of Dihalogens XY with Lewis Bases B in the Gas Phase: A Systematic Case for the Halogen Analogue B⋅⋅⋅XY of the Hydrogen Bond B⋅⋅⋅HX

Legon

1999

Angew. Chem. Int. Ed.

635

443

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Similar and yet also notably different are the B small middle dot small middle dot small middle dotXY and B small middle dot small middle dot small middle dotHX complexes in the gas phase, where B is a simple Lewis base, XY is a homo- or heterodihalogen molecule, and HX is a hydrogen halide. This is demonstrated, for example, by the structures of oxirane small middle dot small middle dot small middle dotClF and oxirane small middle dot small middle dot small middle dotHCl (see picture). Both bonds are dominated by simple electrostatic interactions, but differ in terms of their propensity for nonlinearity.

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Section: The Halogen Bond B´´´xy and How To Encourage Charge Transfermentioning

confidence: 93%

Prereactive Complexes of Dihalogens XY with Lewis Bases B in the Gas Phase: A Systematic Case for the Halogen Analogue B⋅⋅⋅XY of the Hydrogen Bond B⋅⋅⋅HX

Legon

1999

Angew. Chem. Int. Ed.

635

443

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“…Although the values of v zz , p c , and i c of Cl-NO 2 [13] are almost the same as those of CH 2 @N-Cl [12], the r(N-Cl) of the former is longer than that of the latter by 0.092(6) Å. The values of p c and i c of Cl-NO 2 are 5% and 14%, respectively, and therefore the single bond character is 81%.…”

Section: Bond Length Of N-cl and 35 CL Quadrupole Coupling Constantsmentioning

confidence: 77%

“…It is interesting that the bond lengths of N-Cl, r(N-Cl), of Cl-NX (X = CO [11], H 2 [3], CH 2 [12], O 2 [13], and O [14]) tend to shorten or lengthen by changing the substituted group (X). Cazzoli et al reported the r(N-Cl) and 35 Cl nuclear quadrupole coupling constants of v zz , v yy , and v xx , in which the z-direction is taken to the N-Cl bond and the v yy is equal to the v bb [3].…”

Section: Bond Length Of N-cl and 35 CL Quadrupole Coupling Constantsmentioning

confidence: 99%

Microwave spectra, inversion splittings and quadrupole coupling constants of NHDCl and ND2Cl

Masuko¹,

Hamada²,

Mizoguchi³

et al. 2009

Journal of Molecular Spectroscopy

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“…For ClNO 2 , the calculated values of the ClÀN and NÀO bond lengths at the B3LYP/6-311 + G(3df) level, which are only 0.011 longer and 0.012 shorter, respectively, than those obtained at the CCSD(T)/TZ2P level, are in reasonable agreement with the experimental data. [29] For cis-ClONO and trans-ClONO, the single OÀN bonds calculated at the B3LYP/6-311 + G(3df) level are 0.076 and 0.020 shorter, respectively and the ClON bond angles around 38 larger than those calculated at the CCSD(T)/TZ2P level. A comparison of the predicted frequencies of ClNO 2 , cis-ClONO, and trans-ClONO at the B3LYP/6-311 + G(3df) level with available experimental data and with the values computed by Lee [17] at the CCSD(T)/TZ2P level is presented in Table 1.…”

Section: Isomers Of Clonomentioning

confidence: 96%

Ab Initio Studies of ClO_x Reactions: Prediction of the Rate Constants of ClO+NO for the Forward and Reverse Processes

Zhu

Lin

2004

ChemPhysChem

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The mechanisms for ClO+NO and its reverse reactions were investigated by means of ab initio molecular orbital and statistical theory calculations. The species involved were optimized at the B3LYP/6-311 +G(3df) level, and their energies were refined at the CCSD(T)/6-311+ G(3df)//B3LYP/6-311 + G(3df) level. Five isomers and the transition states among them were located. The relative stability of these isomers is ClNO2 > cis-ClONO > trans-ClONO > cis-OClNO>trans-OClNO. The heats of formation of the three most-stable isomers were predicted using isodesmic reactions by different methods. The predicted bimolecular reaction rate constant shows that, below 100 atm, the formation of Cl+NO2 is dominant and pressure-independent. The total rate constant can be expressed as: k(ClO+NO)= 1.43 x 10(-9)T(-083)exp(92/ T) cm3 molecule(-1)s(-1) in the temperature range of 200-1000 K, in close agreement with experimental data. For the reverse reaction, Cl+NO2-->ClNO2 and ClONO (cis and trans isomers), the sum of the predicted rate constants for the formation of the three isomers and their relative yields also reproduce the experimental data well. The predicted total third-order rate constants in the temperature range of 200-1000 K can be represented by: k0(He) = 4.89 x 10(-6)T(-5.85) exp(-796/T) cm6 molecule(-1)s(-1) and k0(N2) =5.72 x 10(-15)T(-5.80) exp(-814/T) cm6 molecule(-1)s(-1). The predicted high- and low-pressure limit decomposition rates of CINO2 in Ar in the temperature range 400-1500 K can be expressed, respectively, by: k-(ClNO2) = 7.25 x 10(19)T(-1.89) exp(-16875/T) s(-1) and kd(ClNO2) = 2.51 x 10(38)T(-6.8) exp(-18409/T) cm3 molecule(-1) s(-1). The value of k0(ClNO2) is also in reasonable agreement with available experimental data.

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64. The microwave spectrum, structure, and dipole moment of nitryl chloride

Cited by 35 publications

References 0 publications

Prereactive Complexes of Dihalogens XY with Lewis Bases B in the Gas Phase: A Systematic Case for the Halogen Analogue B⋅⋅⋅XY of the Hydrogen Bond B⋅⋅⋅HX

Prereactive Complexes of Dihalogens XY with Lewis Bases B in the Gas Phase: A Systematic Case for the Halogen Analogue B⋅⋅⋅XY of the Hydrogen Bond B⋅⋅⋅HX

Microwave spectra, inversion splittings and quadrupole coupling constants of NHDCl and ND2Cl

Ab Initio Studies of ClO_x Reactions: Prediction of the Rate Constants of ClO+NO for the Forward and Reverse Processes

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64. The microwave spectrum, structure, and dipole moment of nitryl chloride

Cited by 35 publications

References 0 publications

Prereactive Complexes of Dihalogens XY with Lewis Bases B in the Gas Phase: A Systematic Case for the Halogen Analogue B⋅⋅⋅XY of the Hydrogen Bond B⋅⋅⋅HX

Prereactive Complexes of Dihalogens XY with Lewis Bases B in the Gas Phase: A Systematic Case for the Halogen Analogue B⋅⋅⋅XY of the Hydrogen Bond B⋅⋅⋅HX

Microwave spectra, inversion splittings and quadrupole coupling constants of NHDCl and ND2Cl

Ab Initio Studies of ClOx Reactions: Prediction of the Rate Constants of ClO+NO for the Forward and Reverse Processes

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Ab Initio Studies of ClO_x Reactions: Prediction of the Rate Constants of ClO+NO for the Forward and Reverse Processes