title: Comparative study of mono- and dinuclear complexes of late 3d-metal chlorides with N,N-dimethylformamide in the gas phase.
abstract: Mono- and binuclear complexes of N,N-dimethylformamide (DMF) with chlorides of the divalent, late 3d metals M = Co, Ni, Cu, and Zn are investigated by means of electrospray ionization (ESI). Specifically, ESI leads to monocations of the type [(DMF)(n)MCl](+) and [(DMF)(n)M(2)Cl(3)](+), of which the species with n = 2 and 3 were selected for in-depth studies. The latter include collision-induced dissociation experiments, gas-phase infrared spectroscopy, and calculations using density functional theory. The mononuclear complexes [(DMF)(n)MCl](+) almost exclusively lose neutral DMF upon collisional activation with the notable exception of the copper complex, for which also a reduction from Cu(II) to Cu(I) concomitant with the release of atomic chlorine is observed. For the dinuclear clusters, there exists a competition between loss of a DMF ligand and cluster degradation via loss of neutral MCl(2) with decreasing cluster stability from cobalt to zinc. For the specific case of [(DMF)(n)ZnCl](+) and [(DMF)(n)Zn(2)Cl(3)](+), ion-mobility mass spectrometry indicates the existence of two isomeric cluster ions in the case of [(DMF)(2)Zn(2)Cl(3)](+) which corroborates parallel theoretical predictions.
authors.affiliation: Institute of Organic Chemistry and Biochemistry, Prague, Czech Republic.
authors.forename: Lucie
authors.initials: L
authors.lastname: Duchácková
authors.forename: Jana
authors.initials: J
authors.lastname: Roithová
authors.forename: Petr
authors.initials: P
authors.lastname: Milko
authors.forename: Jan
authors.initials: J
authors.lastname: Zabka
authors.forename: Nikos
authors.initials: N
authors.lastname: Tsierkezos
authors.forename: Detlef
authors.initials: D
authors.lastname: Schröder
mesh_terms: D002712:Chlorides / Q000737:chemistry*; D003035:Cobalt / Q000737:chemistry; D003300:Copper / Q000737:chemistry; D004126:Dimethylformamide; D005559:Formamides / Q000737:chemistry*; D005740:Gases / Q000737:chemistry; D008670:Metals / Q000737:chemistry*; D008958:Models, Molecular; D009532:Nickel / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D015032:Zinc / Q000737:chemistry
chemical_list: D002712:Chlorides; D005559:Formamides; D005740:Gases; D008670:Metals; D003035:Cobalt; D003300:Copper; D009532:Nickel; D004126:Dimethylformamide; D015032:Zinc