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Interconversion of FeC{sub 2}H{sub 3}{sup +} and HFeC{sub 2}H{sub 2}{sup +}: An FTICR and density functional study

Journal Article · · Organometallics
DOI:https://doi.org/10.1021/om9902941· OSTI ID:20013625

The geometries and energetics of four FeC{sub 2}H{sub 3}{sup +} isomers have been studied by a hybrid of density functional theory (DFT) and the Hartree-Fock approach (BECKE3LYP). The bond dissociation energy D{degree}(FeH{sup +}-C{sub 2}H{sub 2}) for the quintet ground state is predicted to be 32.9 kcal/mol, which compares well with the experimentally measured D{degree}(Fe{sup +}-C{sub 2}H{sub 2}) value of 32 kcal/mol. The [Fe, C{sub 2}, H{sub 3}]{sup +} system is also studied experimentally by using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). In situ synthesis of FeC{sub 2}H{sub 3}{sup +} is achieved by a complex, multistep procedure involving ion/molecule reactions in conjunction with CID and SORI-CID techniques. Kinetics for H/D exchange reactions between FeH{sup +}/FeD{sup +} and C{sub 2}D{sub 4}/C{sub 2}H{sub 4} are also measured and provide complementary information to Schwarz's studies of the [Fe, C{sub 2}, H{sub 5}]{sup +} system.

Research Organization:
Purdue Univ., West Lafayette, IN (US)
Sponsoring Organization:
US Department of Energy
DOE Contract Number:
FG02-87ER13766
OSTI ID:
20013625
Journal Information:
Organometallics, Journal Name: Organometallics Journal Issue: 26 Vol. 18; ISSN 0276-7333; ISSN ORGND7
Country of Publication:
United States
Language:
English

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