Mass Spectrometric Studies of Reductive Elimination from Pd(IV) Complexes

Abstract

Reductive elimination of ethane from the palladium(IV) complex [PdMe3(bpy)I] (bpy = 2,2'-bipyridine) is studied by electrospray ionization mass spectrometry. Palladium(IV) complexes can be detected as binuclear clusters [Pd2Me6I(bpy)2](+) or as complexes [PdMe3(bpy)(L)](+) stabilized by an electron-donating ligand L. Fragmentation of all palladium(IV) complexes is dominated by elimination of ethane which corresponds to the reductive elimination coupling of the methyl groups. The associated energy demands for different complexes reveal that the mononuclear complexes with poorly electron-donating ligands provide the fastest reaction.

Anti-cancer organoruthenium(ii) complexes and their interactions with cysteine and its analogues. A mass-spectrometric study

“…After establishing the importance of the pta units for the stability of the ruthenium complexes, we compared the binding energies of different ligands in ruthenium complexes in energy-resolved collision-induced dissociation (CID) experiments. 16 …”

Periodic Trends Manifested through Gas-Phase Generation of Anions Such as [AlH4]−, [GaH4]−, [InH4]−, [SrH3]−, [BaH3]−, [Ba(0)(η2-O2CH)1]−, [Pb(0)H]−, [Bi(I)H2]−, and Bi– from Formates

“…To form the m/z 205 ion (13b), the [H−In(III)(η-OCOH) 3 ] − ion (9c) should undergo a reductive elimination reaction. Even though there are many examples of reductive eliminations from organometallic cations in the gas phase,61,62 the reductive elimination of elements of HCOOH described here is rather unusual. Apparently, the m/z 251 ion (9c) undergoes simultaneous oxidation to H 2 (or HCOOH), whereas the indium core undergoes a reduction from oxidation state +3 to +1 (Scheme 3).…”

Observation and Characterization of Single Elementary Reactions of Organometallics

“…Hyvl and Roithováinvestigated the liberation of ethane from a series of ligated trimethylpalladium(IV) cations, including systems, whose charge was located on a spectator ligand (Figure 9). 60 Energy-dependent fragmentation experiments provided information on the relative propensities of the different complexes toward the reductive elimination of ethane. As expected, electron-poor ligands facilitated this reaction.…”