Gas-phase synthesis and reactivity of binuclear gold hydride cations, (R3PAu)2H+ (R = Me and Ph).
Electrospray ionization of a mixture of the two gold phosphine chlorides, R3PAuCl (R = Ph and Me), silver nitrate and the amino acid N,N-dimethylglycine (DMG) yields a range of gold containing cluster ions including: (R3P)Au(PR'3)+; (R3PAu)(R'3PAu)Cl+ and (R3PAu)(R'3PAu)(DMG-H)+ (where R = R' = Ph; R = R' = Me; R = Me and R' = Ph). Collision induced dissociation (CID) of the (R3PAu)(R'3PAu)(DMG-H)+ precursor ions yielded the hitherto unknown gold hydride dimers (R3PAu)(R'3PAu)H+. The gas-phase chemistry of these dimers was studied using ion-molecule reactions, collision induced dissociation, electronic excitation dissociation (EED) and DFT calculations on the (H3PAu)2H+ model system. A novel phosphine ligand migration was found to occur prior to fragmentation under CID conditions and this was supported by DFT calculations, which revealed a transition state with a bridging phosphine ligand.
Khairallah
George N
GN
School of Chemistry, University of Melbourne, Victoria 3010, Australia.
O'Hair
Richard A J
RA
Bruce
Michael I
MI
D002412:Cations / Q000737:chemistry; D018360:Crystallography, X-Ray; D017357:Cyclotrons; D004563:Electrochemistry; D005583:Fourier Analysis; D013058:Mass Spectrometry; D008956:Models, Chemical; D008958:Models, Molecular; D015233:Models, Statistical; D050607:Organogold Compounds / Q000138:chemical synthesis*; D010720:Phosphines / Q000138:chemical synthesis / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization
D002412:Cations; D050607:Organogold Compounds; D010720:Phosphines