Gas-phase ion–molecule reactions of divalent metal complex ions: Toward coordination structure analysis by mass spectrometry and some intrinsic coordination chemistry along the way

Combariza, Marianny Y.; Fahey, Angela M.; Milshteyn, Aleksandr; Vachet, Richard W.

doi:10.1016/j.ijms.2005.05.006

Cited by 49 publications

(29 citation statements)

References 64 publications

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“…However, on looking at terminal complexes, doubts may arise about which atoms of the ligands were initially coordinated to the metal. CID experiments on their own may be limited by the inability to establish whether a fragment lost during CID was coordinatedátoátheámetaláatátheábeginningáoránotá [57].…”

Section: Esi-msástudiesáofácu(ii)-ureaácomplexáformationáalso Reportementioning

confidence: 99%

Complexation of transition metals by 3-azidopropionitrile. An electrospray ionization mass spectrometry study

Couto

Duarte

Fernandez

et al. 2007

J. Am. Soc. Mass Spectrom.

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Most complexes of azides and transition metals involve the N 3Ϫ azide anion as a ligand other than an organic azide. Complexes of organic azides with metals are involved in biological applications and in the deposition of nitrenes on metal surfaces, producing nitride layers for semi-conductors preparation; this makes the study of these interactions an important issue. This work describes a study of the complexation of nickel and cobalt by 3-azidopropionitrile by means of electrospray ionization mass spectrometry (ESI-MS). Complexes were obtained from solutions of NiCl 2 and CoCl 2 in methanol/water. In the case of nickel, other NiX 2 salts were investigated (where X ϭ Br or NO 3 ) and other solvents were also studied (notably ethanol/water). All complexes detected were single positively charged, with various stoichiometries, some resulted from the fragmentation of the ligand, the loss of N 2 , and HCN being quite common. The most abundant cations observed were [Ni(II)AzAzX] ϩ , where X ϭ Cl, Br, NO 3 . Some of the complexes showed solvation with methanol/ethanol/water. Metal reduction was observed in complexes where a radical was lost, resulting from the homolytic cleavage of a metalOnitrogen bond. Collision induced dissociation (CID) experiments followed by tandem mass spectrometry (MS-MS) analysis were not absolutely conclusive about the coordination site. However, terminal ions observed from the fragmentation routes were explained by a proposed gas-phase mechanism. Density functional theory calculations were carried out and provided structures for some complexes, pointing to the possibility of 3-azidopropionitrile acting as a mono-or a bidentate ligand. (J Am Soc Mass Spectrom 2007, 18, 453-465)

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Section: Esi-msástudiesáofácu(ii)-ureaácomplexáformationáalso Reportementioning

confidence: 99%

Complexation of transition metals by 3-azidopropionitrile. An electrospray ionization mass spectrometry study

Couto

Duarte

Fernandez

et al. 2007

J. Am. Soc. Mass Spectrom.

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“…Over the past decade electrospray ionization mass spectrometry (ESI-MS) has been successfully employed to investigate structural features, intrinsic stabilities and reactivities of multiply-charged coordination compounds of the first-row transition-metal dications [1][2][3][4][5][6][7][8]. Polyamino complexes of the latter have attracted attention due to the relatively high concentrations of polyamines in vivo where they are present as protonated or metallated complexes rather than as free ligands.…”

Section: Introductionmentioning

confidence: 99%

An investigation of the dissociation of complexes of triethylene tetramine with first-row transition-metal dications by electrospray ionization tandem mass spectrometry: Remote CC bond activation

Anichina

Böhme

2007

International Journal of Mass Spectrometry

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“…[1][2][3] The particularly unique features of electrospray ionization (ESI) [4,5] mass spectrometry offer the option to address the topic of solvation directly. [6][7][8][9] Here, we report a systematic ESI study of the cationic complexes formed from solutions of FeCl 3 in alcoholic solvents. [10] FeCl 3 was chosen as a readily soluble salt of a redox-active metal.…”

Section: Introductionmentioning

confidence: 99%

Innocent and Less‐Innocent Solvent Ligands: A Systematic Investigation of Cationic Iron Chloride/Alcohol Complexes by Electrospray Ionization Mass Spectrometry Complemented by DFT Calculations

Trage¹,

Diefenbach²,

Schröder³

et al. 2006

Chemistry A European J

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The influence of anionic and neutral ligands on the reactivity of cationic iron complexes towards methanol, ethanol, and iso- and n-propanol has been investigated by means of electrospray ionization (ESI) mass spectrometry, and in key questions the experimental results are supported by DFT calculations. The chemical processes taking place when FeCl2+ is coordinated to a variable number of alcohol molecules were investigated by collision experiments, as well as reactivity and labeling studies. The most abundant cations formed upon ESI of FeCl3/ROH mixtures can be described as consisting of a covalently bound FeCl2+ core, which is stabilized by neutral ROH ligands, for example, FeCl2(CH3OH)n+. Indications for a hydrogen-bonding mechanism of ligands in the second coordination sphere are given by the observation of the formally hypercoordinated ion FeCl2(CH3OH)5+ and interpretation of kinetic data for n=4. Further, deuterium labeling experiments disclose a number of hidden hydrogen transfers and imply that complexes with n=1 and 2 can exist in two tautomeric forms. Upon change of the alcohol ligand from methanol to ethanol and propanol, additional reaction pathways become accessible, among which metal-assisted dehydration of the respective alcohols by means of an ion/dipole mechanism is the most important.

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Gas-phase ion–molecule reactions of divalent metal complex ions: Toward coordination structure analysis by mass spectrometry and some intrinsic coordination chemistry along the way

Cited by 49 publications

References 64 publications

Complexation of transition metals by 3-azidopropionitrile. An electrospray ionization mass spectrometry study

Complexation of transition metals by 3-azidopropionitrile. An electrospray ionization mass spectrometry study

An investigation of the dissociation of complexes of triethylene tetramine with first-row transition-metal dications by electrospray ionization tandem mass spectrometry: Remote CC bond activation

Innocent and Less‐Innocent Solvent Ligands: A Systematic Investigation of Cationic Iron Chloride/Alcohol Complexes by Electrospray Ionization Mass Spectrometry Complemented by DFT Calculations

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