title: Interaction of metal cations with alkylnitriles in the gas phase: solvation of metal ions by the hydrocarbon chain.
abstract: Relative affinity measurements of monovalent metal ions (M = Li(+), Na(+), Cu(+)and Ag(+)) toward aliphatic nitriles have been performed using the kinetic method by dissociation of metal bound dimer ions of the type R1C≡N-M(+)-N≡CR(2). It is found, particularly for Cu(+) and Ag(+), that the affinity towards nitriles having long chains (>C(6)) is markedly enhanced. This is attributed to a bidentate interaction of the metal ion with the nitrile moiety and the aliphatic chain. Theoretical calculations on the copper complexes show that these bidentate structures enjoy about 30% greater copper ion affinities compared to their linear counterparts. Such aliphatic interactions also play a major role in the dissociation chemistry of copper bound tetramers of the kind (RC≡N)(4)Cu(2+∙) where the long aliphatic chain R curls around the copper ion to facilitate electron transfer or a redox reaction to produce (RC≡N)(2)Cu(+) + RC≡N(+∙) + RC≡N.
authors: Ontar io Ministry of the Environment and Climate Change, 125 Resources Road, Toronto, Ontario M9P 3V6, Canada. Department of Chemistry and Chemical Biology, McMaster University, Hamilton, Ontario L8S 4M1, Canada. karl.jobst@ontario.ca.
authors: Karl J
authors: KJ
authors: Jobst
authors: Department of Chemistry and Chemical Biology, McMaster University, Hamilton, Ontario L8S 4M1, Canada. terlouwj@mcmaster.ca.
authors: Johan K
authors: JK
authors: Terlouw
authors: Department of Neurology, Laboratory of Neuro-Oncology, Erasmus Medical Center, 3015 CN, The Netherlands. t.luider@erasmusmc.nl.
authors: Theo
authors: T
authors: Luider
authors: Department of Neurology, Laboratory of Neuro-Oncology, Erasmus Medical Center, 3015 CN, The Netherlands. Department of Surgery, Erasmus Medical Center, 3015 CN, The Netherlands. n.vanhuizen@erasmusmc.no.
authors: Nick A
authors: NA
authors: van Huizen
authors: D epartment of Neurology, Laboratory of Neuro-Oncology, Erasmus Medical Center, 3015 CN, The Netherlands. p.burgers@erasmusmc.nl.
authors: Peter C
authors: PC
authors: Burgers