Large effect of a small substitution: competition of dehydration with charge retention and coulomb explosion in gaseous [(bipy(R))Au(mu-O)2Au(bipy(R))]2+ dications.
Dinuclear gold(III) clusters with a rhombic Au(2)O(2) core and 2,2'-bipyridyl ligands substituted in the 6-position (bipy(R)) are examined by tandem mass spectrometry. Electrospray ionization of the hexafluorophosphate salts affords the complexes [(bipy(R))Au(mu-O)(2)Au(bipy(R))](2+) as free dications in the gas phase. The fragmentation behavior of the mass-selected dications is probed by means of collision-induced dissociation experiments which reveal an exceptionally pronounced effect of substitution. Thus, for the parent compound with R = H, i.e., [(bipy)Au(mu-O)(2)Au(bipy)](2+), fragmentation at the dicationic stage prevails to result in a loss of neutral H(2)O concomitant with an assumed rollover cyclometalation of the bipyridine ligands. In marked contrast, all complexes with alkyl substituents in the 6-position of the ligands (bipy(R) with R = CH(3), CH(CH(3))(2), CH(2)C(CH(3))(3), and 2,6-C(6)H(3)(CH(3))(2)) as well as the corresponding complex with 6,6'-dimethyl-2,2'-dipyridyl as a ligand exclusively undergo Coulomb explosion to produce two monocationic fragments. It is proposed that the additional steric strain introduced to the central Au(2)O(2) core by the substituents on the bipyridine ligand, in conjunction with the presence of oxidizable C-H bonds in the substituents, crucially affects the subtle balance between dication dissociation under maintenance of the 2-fold charge and Coulomb explosion into two singly charged fragments.
Tyo
Eric C
EC
Department of Chemistry, Pennsylvania State University, University Park, Pennsylvania 16802, USA.
Castleman
A W
AW
Schröder
Detlef
D
Milko
Petr
P
Roithova
Jana
J
Ortega
Jean Michel
JM
Cinellu
Maria Agostina
MA
Cocco
Fabio
F
Minghetti
Giovanni
G
D015082:2,2'-Dipyridyl / Q000032:analysis* / Q000737:chemistry; D008024:Ligands; D015394:Molecular Structure; D050607:Organogold Compounds / Q000032:analysis* / Q000737:chemistry; D053719:Tandem Mass Spectrometry
D008024:Ligands; D050607:Organogold Compounds; D015082:2,2'-Dipyridyl