Gaseous Cl3+ and Cl2F+ cations. a joint mass spectrometric and theoretical study

Cacace, Fulvio; Petris, Giulia de; Pepi, Federico; Rosi, Marzio; Sgamellotti, Antonio

doi:10.1002/(sici)1097-0231(19981215)12:23<1911::aid-rcm398>3.0.co;2-2

Cited by 6 publications

(7 citation statements)

References 10 publications

(19 reference statements)

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“…60, oP80, 60d 8 c 3 a)w ith a = 11.9269 (7), b = 11.5370 (7), c = 12.0640(6) , V = 1660.01(16) 3 , Z = 8a t1 00 K. Interestingly, the compound is not isotypic to the previously reported [Br 3 ] [AsF 6 ]( space group P " 1). [101] We note that the cell volume is ap- [85][86][87][88] [Cl 4 ] + [89] [ClF 2 ] + , [90][91][92] [Cl 2 F] + , [87,93,94] [ClF 4 ] + , [95,96] [99][100][101] [Br 5 ] + [101,102] [BrF 2 ] + , [103,104] [BrF 4 ] + , [105,106] [BrF 6 ] + , [107] [Br 2 F 5 ] + , [12] [Br 3 F 8 ] + [12] [100,108,109] [I 5 ] + , [109] [I 7 ] + (unsure) [110] [I 4 ] 2 + , [111,112] [IF 2 ] + , [114] [ICl 2 ] + , [115,116] [IBrCl] + , [117] [IBr 2 ] + , [118] [I 2 Cl] + (unsure), [119] [I 2 Br] + , [120] [IF 4 ] + , [105] [I 3 Cl 2 ] + , [119] [IF 6 ] + , [121] [I 4 Cl 3 ] + (unsure),…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of [Br₃][MF₆] (M=Sb, Ir), as well as Quantum Chemical Study of [Br₃]⁺ Structure, Chemical Bonding, and Relativistic Effects Compared with [XBr₂]⁺ (X=Br, I, At, Ts) and [TsZ₂]⁺ (Z=F, Cl, Br, I, At, Ts)

Ivlev

Gaul

Chen

et al. 2019

Chemistry A European J

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[Br3][SbF6] and [Br3][IrF6] were synthesized by interaction of BrF3 with Sb2O3 or iridium metal, respectively. The former compound crystallizes in the orthorhombic space group Pbcn (No. 60) with a=11.9269(7), b=11.5370(7), c=12.0640(6) Å, V=1660.01(16) Å3, Z=8 at 100 K. The latter compound crystallizes in the triclinic space group Ptrue1‾ (No. 2) with a=5.4686(5), b=7.6861(8), c=9.9830(9) Å, α=85.320(8), β=82.060(7), γ=78.466(7)°, V=406.56(7) Å3, Z=2 at 100 K. Both compounds contain the cation [Br3]+, which has a bent structure and is coordinated by octahedron‐like anions [MF6]− (M=Sb, Ir). Experimentally obtained cell parameters, bond lengths, and angles are confirmed by solid‐state DFT calculations, which differ from the experimental values by less than 2 %. Relativistic effects on the structure of the tribromonium(1+) cation are studied computationally and found to be small. For the heaviest analogues containing At and Ts, however, pronounced relativistic effects are found, which lead to a linear structure of the polyhalogen cation.

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Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of [Br₃][MF₆] (M=Sb, Ir), as well as Quantum Chemical Study of [Br₃]⁺ Structure, Chemical Bonding, and Relativistic Effects Compared with [XBr₂]⁺ (X=Br, I, At, Ts) and [TsZ₂]⁺ (Z=F, Cl, Br, I, At, Ts)

Ivlev

Gaul

Chen

et al. 2019

Chemistry A European J

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“…In the second step the cation can be trapped by either neutrals, according to Equations 1a and 2b yielding the observed products, namely b and protonated methyl chloride. As to the energetics of the process, the dissociative hydrideion abstraction, as shown in Equation (8), is estimated to be endothermic by 5.5 kcal mol À1 , based on available thermochemical data [8,18]…”

Section: Discussionmentioning

confidence: 99%

Gaseous [H3C−Cl−Cl]+ Ions from the Reaction of Methane with Cl3+, the First Example of a New Dihalogenation Process: Formation and Characterization of CH3Cl2+ Isomers by Experimental and Theoretical Methods

et al. 1999

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The structure, stability, and reactivity of the [C,H 3 ,Cl 2 ] ions from the reaction of Cl 3 with CH 4 were studied by structurally diagnostic mass spectrometric techniques and by computational methods. The ionic products were characterized as protonated dichloromethane [ClH 2 CÀClH] (1), the more stable isomer, that behaves exclusively as a Brùnsted acid, and the hitherto unknown [H 3 CÀClÀCl] ion (2), a chlorinating and methylating cation. Formation of 2 is the first example of a new class of electrophilic substitution, in which a single H atom is replaced by the diatomic [ClÀCl] dichlorinium ion. In addition, the proton affinity of dichloromethane was determined by experimental and theoretical methods to be 150.2 AE 2 and 151 kcal mol À1 , respectively.

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“…Cl 3 + is formed in the doped He droplets as well with about an order of magnitude less intensity. The formation of the Cl 3 + cation was reported in the literature by chlorine chemical ionization via the exothermic reaction of Cl + transfer from Cl 2 2+ to chlorine or by the endothermic reaction of Cl 2 + with chlorine [34]. In He droplets doped with clusters of CCl 4 the same reactions are likely to occur as Cl 2 and Cl 2 + can be formed via collisions of CCl 4 with He + and He*.…”

mentioning

confidence: 89%

Electron impact ionization of CCl4 and SF6 embedded in superfluid helium droplets

Schöbel

Dampc

Silva

et al. 2009

International Journal of Mass Spectrometry

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Gaseous Cl3+ and Cl2F+ cations. a joint mass spectrometric and theoretical study

Cited by 6 publications

References 10 publications

Synthesis and Characterization of [Br₃][MF₆] (M=Sb, Ir), as well as Quantum Chemical Study of [Br₃]⁺ Structure, Chemical Bonding, and Relativistic Effects Compared with [XBr₂]⁺ (X=Br, I, At, Ts) and [TsZ₂]⁺ (Z=F, Cl, Br, I, At, Ts)

Synthesis and Characterization of [Br₃][MF₆] (M=Sb, Ir), as well as Quantum Chemical Study of [Br₃]⁺ Structure, Chemical Bonding, and Relativistic Effects Compared with [XBr₂]⁺ (X=Br, I, At, Ts) and [TsZ₂]⁺ (Z=F, Cl, Br, I, At, Ts)

Gaseous [H3C−Cl−Cl]+ Ions from the Reaction of Methane with Cl3+, the First Example of a New Dihalogenation Process: Formation and Characterization of CH3Cl2+ Isomers by Experimental and Theoretical Methods

Electron impact ionization of CCl4 and SF6 embedded in superfluid helium droplets

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Gaseous Cl3+ and Cl2F+ cations. a joint mass spectrometric and theoretical study

Cited by 6 publications

References 10 publications

Synthesis and Characterization of [Br3][MF6] (M=Sb, Ir), as well as Quantum Chemical Study of [Br3]+ Structure, Chemical Bonding, and Relativistic Effects Compared with [XBr2]+ (X=Br, I, At, Ts) and [TsZ2]+ (Z=F, Cl, Br, I, At, Ts)

Synthesis and Characterization of [Br3][MF6] (M=Sb, Ir), as well as Quantum Chemical Study of [Br3]+ Structure, Chemical Bonding, and Relativistic Effects Compared with [XBr2]+ (X=Br, I, At, Ts) and [TsZ2]+ (Z=F, Cl, Br, I, At, Ts)

Gaseous [H3C−Cl−Cl]+ Ions from the Reaction of Methane with Cl3+, the First Example of a New Dihalogenation Process: Formation and Characterization of CH3Cl2+ Isomers by Experimental and Theoretical Methods

Electron impact ionization of CCl4 and SF6 embedded in superfluid helium droplets

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Synthesis and Characterization of [Br₃][MF₆] (M=Sb, Ir), as well as Quantum Chemical Study of [Br₃]⁺ Structure, Chemical Bonding, and Relativistic Effects Compared with [XBr₂]⁺ (X=Br, I, At, Ts) and [TsZ₂]⁺ (Z=F, Cl, Br, I, At, Ts)

Synthesis and Characterization of [Br₃][MF₆] (M=Sb, Ir), as well as Quantum Chemical Study of [Br₃]⁺ Structure, Chemical Bonding, and Relativistic Effects Compared with [XBr₂]⁺ (X=Br, I, At, Ts) and [TsZ₂]⁺ (Z=F, Cl, Br, I, At, Ts)