Gas-Phase Chemistry of Pentacoordinate Silicon Hydride Ions

Hajdasz, David J.; Ho, Yeunghaw; Squires, Robert R.

doi:10.1021/ja00102a045

Cited by 45 publications

(32 citation statements)

References 2 publications

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“…lines rationalizing the super-tetrahedroni n4 2 + as sp 3 ,a nd being relatedt oC H 4 or generalized as AX 4 , [27,28] it is reasonable to argue that 3a + would correspond to trigonal bipyramidal SiH 5 À , [49] NH 5 , [50] PH 5 , [51] or generalized to an AX 5 molecule as shown in Figure 10.…”

Section: Characterization By Ir Spectroscopymentioning

confidence: 92%

Altering Charges on Heterobimetallic Transition‐Metal Carbonyl Clusters

Unkrig

Kloiber

Butschke

et al. 2020

Chemistry A European J

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The homoleptic group 5c arbonylates [M(CO) 6 ] À (M = Nb, Ta)s erve as ligands in carbonyl-terminated heterobimetallic Ag m M n clusters containing 3t o1 1m etal atoms. Based on our serendipitous [Ag 6 {Nb(CO) 6 } 4 ] 2 + (4a 2 +)p recedent, we established accesst os uch Ag m M n clusters of the composition [Ag m {M(CO) 6 } n ] x (M = Nb, Ta ; m = 1, 2, 6; n = 2, 3, 4, 5; x = 1À,1+ ,2+). Salts of those molecularc luster ions were synthesized by the reaction of [NEt 4 ][M(CO) 6 ]and Ag[Al(OR F) 4 ](R F = C(CF 3) 3)i nt he corrects toichiometry in 1,2,3,4tetrafluorobenzene at À35 8C. The solid-state structures were determined by single-crystal X-ray diffractionm ethods and, owing to the thermali nstability of the clusters, al imited scope of spectroscopicm ethods. In addition, DFT-based AIM calculations were performed to provide an understanding of the bonding within these clusters. Apparently,t he clusters 3 + (m = 6, n = 5) and 4 2 + (m = 6, n = 4) are superatom complexes with trigonal-prismatic or octahedral Ag 6 superatom cores. The [M(CO) 6 ] À ions then bind through three CO units as tridentate chelate ligands to the superatom core, giving overall structures related to tetrahedral AX 4 (4 2 +)o rt rigonal bipyramidal AX 5 molecules (3 +).

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Section: Characterization By Ir Spectroscopymentioning

confidence: 92%

Altering Charges on Heterobimetallic Transition‐Metal Carbonyl Clusters

Unkrig

Kloiber

Butschke

et al. 2020

Chemistry A European J

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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.…”

mentioning

confidence: 99%

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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“…The formation and thermochemical properties of pentacoordinate silicon hydride anions, SiH 5 n X n , have been reported by Squires and coworkers 32,33 . These ions can be generated via the addition of nucleophilic anions to silanes or, in the case of SiH 5 34,35 , via hydride transfer from alkyl silicon hydride anions to SiH 4 in flowing afterglow experiments.…”

Section: Anionic Silicon Speciesmentioning

confidence: 76%

Gas‐Phase Ion Chemistry of Silicon‐Containing Molecules†This article is dedicated to Saul Patai.

Goldberg

Schwarz

2009

Patai's Chemistry of Functional Groups

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Introduction Thermochemistry Ion–Molecule Reactions of Silicon‐Containing Molecules Generation and Characterization of Small Multiply Bonded Silicon‐Containing Ions and their Neutral Counterparts Rearrangements of Organosilicon Ions Doubly Charged Ions Acknowledgments

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Gas-Phase Chemistry of Pentacoordinate Silicon Hydride Ions

Cited by 45 publications

References 2 publications

Altering Charges on Heterobimetallic Transition‐Metal Carbonyl Clusters

Altering Charges on Heterobimetallic Transition‐Metal Carbonyl Clusters

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

Gas‐Phase Ion Chemistry of Silicon‐Containing Molecules†This article is dedicated to Saul Patai.

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