Sequential IRMPD of XGe(OEt)4− ions: Gas-phase synthesis of novel oxy-germanium anions

Xavier, Luciano A.; Malaspina, Thaciana; Morgon, Nelson H.; Menegon, Jair J.; Riveros, José M.

doi:10.1016/j.ijms.2010.11.019

Cited by 3 publications

(1 citation statement)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Because organosilanes and related organometallic species containing Ge, Sn, Ti, and other metals are commonly used as the starting substrates for processes leading to a rich variety of materials, it is important to establish whether this type of exchange reaction can be promoted and extended to other systems. In this respect, the gas-phase ion chemistry and the initial reactivity pattern of Si, Ge, and Ti alkoxides have been previously characterized in these laboratories − to provide some insight on the mechanisms of these reactions. A similar approach has been used in our present work to explore the gas-phase reactivity of R 3 SiO – , R 3 GeO – , and R 3 CO – anions with different potential fluorine donors using FT-ICR mass spectrometry.…”

Section: Introductionmentioning

confidence: 99%

Dynamic/Thermochemical Balance Drives Unusual Alkyl/F Exchange Reactions in Siloxides and Analogs

2016

Self Cite

View full text Add to dashboard Cite

A recent report has shown that siloxides can undergo an unusual Me/F exchange reaction promoted by NF3 in the gas phase ( Angew. Chem. Int. Ed. 2012, 51, 8632-8635). A more extensive study of this kind of exchange has been carried out using mass spectrometry techniques (FT-ICR), DFT calculations, natural bond orbital (NBO) analysis, and Born-Oppenheimer molecular dynamics simulations (BOMD), using NF3, SO2F2, and CF4 as fluorine donors and evaluating the effect of replacing the Si center by Ge and C. This comprehensive approach shows that NF3 is crucial for the exchange reaction, as SO2F2 forms SO3F(-) via a pentacoordinated channel whereas no reaction is observed for CF4. The uniqueness of NF3 is caused by favorable thermochemical consideration and by dynamic effects that preclude the formation of the ubiquitous Si-F pentacoordinated species. Me3GeO(-) was shown to be as reactive as siloxides toward NF3, whereas C analogs showed no reactions under our experimental conditions. The exchange reaction was also shown to take place for triethylsiloxides. These exchange reactions are examples of reaction systems that avoid the lower energy pathway and are driven by dynamic effects that cannot be explained by the potential energy surface.

show abstract