Electrospray mass spectrometric studies of nickel(II)-thiosemicarbazones complexes: Intra-complex proton transfer in the gas phase ligand exchange reactions

2012 ◽  
Vol 321-322 ◽  
pp. 40-48 ◽  
Author(s):  
Kezhi Jiang ◽  
Gaofeng Bian ◽  
Yunfeng Chai ◽  
Huameng Yang ◽  
Quoqiao Lai ◽  
...  
Keyword(s):  
Proton Transfer ◽  
Gas Phase ◽  
Ligand Exchange ◽  
Mass Spectrometric ◽  
Exchange Reactions

Der Einfluß der Kettenlänge auf die massenspektrometrigche Fragmentierung höherer 1.ω-Diphenylalkane / The Influence of the Chain Length on the Mass Spectrometric Fragmentation of Higher 1, ω-Diphenylalkanes

1979 ◽  
Vol 34 (12) ◽  
pp. 1750-1764 ◽  
Author(s):  
Dietmar Kuck ◽  
Hans-Friedrich Grützmacher
Keyword(s):  
Gas Phase ◽  
Chain Length ◽  
Hydrogen Exchange ◽  
Molecular Ions ◽  
Mass Spectrometric ◽  
Exchange Reactions ◽  
Fragment Ions ◽  
Competitive Reactions ◽  
Solvated Ions ◽  
Mass Spectrometric Fragmentation

The mass spectrometric fragmentation of 1,ω-diphenylalkanes (2 ≤ ω ≤ 22) has been studied in order to elucidate the effect of the chain length on the reactions of unstable and metastable molecular ions with respect to the occurrence of internally solvated ions in the gas phase. The unstable molecular ions of all 1,ω-diphenylalkanes react predominantly by formation of C7H7+ and C7H8+ ions, the latter ones are also formed by metastable molecular ions. Neither the variation of the relative abundances of these fragment ions with the chain length nor the fragmentation of specifically deuterated molecular ions indicate any internal solvation in the reacting ions. Inspite of the localized activated C-H bonds at the benzylic positions, these “activated” H atoms are not involved in intra­molecular hydrogen exchange reactions or the formation of C7H8+ ions (with the exception of ω = 3). Especially the higher homologues (co ≿ 12) react very similarly to the molecular ions of 1-phenylalkanes, while the fragmentation of the lower homologues (co ≲ 6) is determined by specific (“vinculoselective”) competitive reactions, e.g. loss of C7H7 and C8H8.

Experimental and Theoretical Investigations into the Mechanisms of Haliranium Ion π-Ligand Exchange Reactions with Cyclic Alkenes in the Gas Phase

2021 ◽  
Author(s):  
Samuel Charles Brydon ◽  
Gabriel da Silva ◽  
Richard OHair ◽  
Jonathan White
Keyword(s):  
Gas Phase ◽  
Ligand Exchange ◽  
Exchange Reactions ◽  
Theoretical Investigations ◽  
Cyclic Alkenes

Haliranium ions are intermediates often involved in complex cyclisations, where their structure allows for control over stereospecific outcomes. Extending previous studies into their structure and reactivity in the gas phase,...

Voltammetric Studies of Some Novel Fe(III) Complexes with Quadridentate Ligands. The Axial Ligand-Exchange Reactions in DMF and DMSO

1995 ◽  
Vol 60 (7) ◽  
pp. 1140-1157 ◽  
Author(s):  
Ljiljana S. Jovanovic ◽  
Luka J. Bjelica
Keyword(s):  
Oxidation State ◽  
Chemical Reactions ◽  
Ligand Exchange ◽  
Kinetic Data ◽  
Central Atom ◽  
Axial Ligand ◽  
Exchange Reactions ◽  
Ligand Effect ◽  
Condensation Products ◽  
Voltammetric Studies

The electrochemistry of four novel Fe(III) complexes of the type [Fe(L)Cl], involving quadridentate ligands based on the condensation products of benzoylacetone-S-methylisothiosemicarbazone with salicylaldehyde, 5-chlorosalicylaldehyde, 3,5-dichlorosalicylaldehyde or 5-nitrosalicylaldehyde, was studied in DMF and DMSO at a GC electrode. All complexes undergo a two-step one-electron reductions, usually complicated by chemical reactions. In solutions containing Cl-, the ligand-exchange reactions Cl--DMF and Cl--DMSO take place. Stability of the chloride-containing complexes was discussed in terms of the coordinated ligand effect, oxidation state of the central atom and, in particular, of the donor effect of the solvent. Some relevant kinetic data were calculated.

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