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|Title:||Sequential IRMPD of XGe(OEt)4− ions: gas-phase synthesis of novel oxy-germanium anions|
|Author:||Xavier, Luciano A.|
Malaspina, Thaciana V.
Morgon, Nelson H.
Menegon, Jair J.
Riveros, José M.
|Abstract:||The gas-phase ion/molecule reactions of F− and EtO− with Ge(OEt)4 yield readily and exclusively pentacoordinated complexes XGe(OEt)4− (X = F, EtO) at pressures in the 10−8 T range as observed by FT-ICR techniques. These hypervalent species are prone to undergo sequential fragmentations induced by infrared multiphoton excitation that lead to a variety of germyl and germanate anions. In the case of FGe(OEt)4−, three primary competitive channels are observed in the IRMPD process that can be identified as (EtO)3GeO−, F(EtO)2GeO− and (EtO)3Ge−. Ab initio calculations have been carried out to characterize the primary fragmentation paths induced by IRMPD and the most favorable structure of the resulting anions. The gas-phase acidity of a number of these germanium-containing ions have been estimated by bracketing experiments and by theoretical calculations. Germanate anions such as (EtO)3GeO− undergo some interesting reactions with H2S to give rise to anions such as (EtO)3GeS− and (EtO)2Ge(OH)S−|
|Appears in Collections:||IQ - Artigos e Outros Documentos|
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