Role of cluster size and substrate in the gas phase CC bond coupling reactions of allyl halides mediated by Agn+ and Agn−1H+ cluster cations

Apparent activation of H2O and elimination of H2 from gas‐phase mixed‐metal complexes containing silver, calcium and deprotonated glycine

“…The reactivity of the species that contain AgH with allyl halides during ion-molecule reactions (IMR) was investigated, and a notable observation made was that carbon-carbon coupling can be achieved via CID of product ions generated by a prior IMR. [23,24] Later, Cheng and coworkers investigated mechanisms by which the glycine is eliminated from the cluster ion precursors, including that the hydride originates from the α-carbon (of glycine ligands) positions. [25] In this study, we employed the method of Khairallah and O'Hair [22] to generate bimetallic complexes [Ag 2 Xx(Gly-H) 3 ] + (where Xx = Mg, Sr, Ca and Ag) for subsequent study of their gas-phase behavior.…”

Gold‐Mediated CI Bond Activation of Iodobenzene

“…This was supported by DFT calculations, which showed that while oxidative addition of iodobenzene to the mononuclear complex Me 3 PAuI has a high activation barrier (132.2 kJ mol À1 ), the related reaction for the bare gold cluster Au 38 has a substantially lower barrier (47.3 kJ mol À1 ). [9] Herein a combination of mass-spectrometry-based experiments and DFT calculations are used to examine the gas phase reactions of iodobenzene with the mononuclear gold cations (R 3 P) n Au + (R = Me, Ph; n = 1, 2) and the ligated gold clusters [Au 3 L n ] + (L = Ph 2 P(CH 2 ) n PPh 2 ; n = 3-6) to establish the molecular requirements for C À I bond activation. [8] The stoichiometry of the metallic reactant ion can be confidently assigned by the unique mass and often-distinctive isotopic signature of the metal.…”

“…Thus, these ions were mass selected and subjected to CID 8)]. (9)]. A further stage of CID on [L n Au 2 I] + results in the loss of AuI [Eq.…”

“…By massselecting the reactant ion, the issue of impurities are circumvented, while reactivity as a function of metal cluster size can simply be probed by examining a range of different clusters. [9] Herein a combination of mass-spectrometry-based experiments and DFT calculations are used to examine the gas phase reactions of iodobenzene with the mononuclear gold cations (R 3 P) n Au + (R = Me, Ph; n = 1, 2) and the ligated gold clusters [Au 3 L n ] + (L = Ph 2 P(CH 2 ) n PPh 2 ; n = 3-6) to establish the molecular requirements for C À I bond activation.…”

Synthesis of ligated-metal species by laser vaporization electrospray ionization (LAVESI)

“…Complexes are formed by electrospraying metal salts with organic and biomolecular ligands. Their gas-phase structure [10][11][12][13][14], reactivity [15][16][17][18], optical properties, etc. are then examined by mass spectrometry.…”