Study of the Gas-phase Chemistry of Y2+ with Small Alkanes

✍ Scribed by Y. Dorothy Hill; Yongqing Huang; Teodor Ast; Ben S. Freiser

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 129 KB
• Volume: 11
• Category: Article
• ISSN: 0951-4198
• DOI: 10.1002/(sici)1097-0231(19970115)11:1<148::aid-rcm819>3.0.co;2-5

✦ Synopsis

Reactions of Y 2 + with C 1 -C 6 alkanes have been examined using a Fourier transform mass spectrometer. Due to the moderate second ionization energy of yttrium, 12.4 eV, mixtures of charge-transfer, hydride-transfer, carbanion-transfer, dehydrogenation and alkane-loss products are observed. There is no observable reaction with methane. The predominant product from the reactions with ethane, propane and butane is YC 2 H 4 2 + . Since Y 2 + has only one valence electron, oxidative addition to form two covalent bonds to the metal center is not possible, and alternative multicentered mechanisms are proposed. YC 2 H 4 2 + undergoes displacement reactions with propane and larger alkanes, indicating that electrostatic forces are mainly involved in the bonding of YC 2 H 4 2 + and other dication products studied, in agreement with theoretical calculations of Bauschlicher and co-workers. In addition to charge-and hydride-transfer, CH 3 -and C 2 H 5 -transfers are also observed in reactions with propane and butane. Charge-and hydride-transfer results are in qualitative agreement with a simple curve-crossing model.