Gas-phase ion chemistry and ion thermochemistry of phenyltrifluorosilane

Krouse, Ian H.; Lardin, Harvey A.; Wenthold, Paul G.

doi:10.1016/s1387-3806(03)00080-0

Cited by 13 publications

(22 citation statements)

References 55 publications

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“…However, because third row and lower main-group elements (e.g., P, S, Cl) readily undergo hypervalent bonding [24], the pentavalent siliconate is a stable intermediate in the reaction and can, in many cases, be observed [25][26][27][28]. Because of their stability, siliconates are often used in fundamental studies of hypervalency [26, 29 -32], as well as in numerous theoretical [33,34] and experimental [7,29,[35][36][37][38][39][40] studies.…”

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“…In continuation of our interest in inorganic main group gas-phase chemistry [27,28], we have studied the formation and decomposition of a series of pentavalent fluorosiliconates, RSi(CH 3 ) 3 F Ϫ . Although there has been some thermochemical characterization of pentavalent siliconates, the effects of substitution are not well known [41].…”

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“…Chloride and fluoride affinities have been reported for some silanes [42][43][44], but there are few other experimental nucleophilic affinities. Most negative ion studies of silanes have focused upon reactivity [45][46][47][48][49] with few studies looking specifically at siliconrelated ion thermochemistry [27,28,43,50].…”

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Fluorotrimethylsilane affinities of anionic nucleophiles: A study of fluoride-induced desilylation

Krouse

Wenthold

2005

J. Am. Soc. Mass Spectrom.

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In this study, preparation and decomposition of five novel pentavalent fluorosiliconates, RSi(CH 3 ) 3 F Ϫ (R ϭ CH 3 CH 2 O, CF 3 CH 2 O, (CH 3 ) 2 CHO, (CH 3 ) 3 SiO, and (CH 3 ) 3 SiNH) is used to investigate the process of fluoride-induced desilylation. The siliconates were characterized by collision-induced dissociation and energy-resolved mass spectrometry. Decomposition of RSi(CH 3 ) 3 F Ϫ leads to loss of the nucleophile R Ϫ and FSi(CH 3 ) 3 , except in the case of (CH 3 ) 3 SiNHSi(CH 3 ) 3 F Ϫ , where HF loss is also observed. Ion affinities for FSi(CH 3 ) 3 have been measured for all five nucleophiles, and compare well with computational predictions. The observed trend of the bond dissociation energies resembles the trend of ⌬H acid values for the corresponding conjugate acids, RH. Additionally, this data has been incorporated with existing thermochemistry to derive fluoride affinities for four of the silanes (R ϭ CH 3 CH 2 O, (CH 3 ) 2 CHO, (CH 3 ) 3 SiO, and (CH 3 ) 3 SiNH). We use the fluoride affinity of the silanes and the FSi(CH 3 ) 3 affinity of the departing nucleophilic anion to assess the feasibility of fluorideinduced desilylation of the silanes examined in this work. (J Am Soc Mass Spectrom 2005, 16, 697-707)

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Fluorotrimethylsilane affinities of anionic nucleophiles: A study of fluoride-induced desilylation

Krouse

Wenthold

2005

J. Am. Soc. Mass Spectrom.

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“…The binding of ions to neutral substrates has been investigated. Krouse et al 32 reported binding energies of fluoride, methoxide, and hydride with phenyltrifluorosilane. The silane is found to be an extremely strong Lewis acid, forming strongly bonded complexes with these ions.…”

Section: B Gas-phase Acidities Anion Stabilities and Neutral Thermoch...mentioning

confidence: 99%

14 Organic gas-phase ion chemistry

Munsch

Wenthold

2004

Annu. Rep. Prog. Chem., Sect. B: Org. Chem.

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“…The scale was fixed at the low end with the fluoride affinity of H 2 O (23.3 kcal/mol) and at the high end with the fluoride affinity of HCO 2 H (45.3 kcal/mol). Energy-resolved collision-induced dissociation (CID) has led to revisions of the fluoride affinity scale allowing the addition of new values [4][5][6].…”

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confidence: 99%