Gas-phase and condensed-phase studies on the reactivity of the azido( 2,2 ': 6 ',2 '-terpyridine) platinum(II) cation

The recent report of the gas-phase loss of nitrogen from [Pt(dien)N-3](+) ( dien = diethylenetriamine) under collision-induced dissociation conditions has prompted us to investigate whether the analogous fragmentation of [Pt(t py)N-3](+) (tpy = 2,2':6',2"-terpyridine) occurs in the gaseous and condens ed phase as well as in the solid state. While such a process occurs in the gaseous phase, attempts to fragment [Pt(tpy)N-3](+) by refluxing it in MeCN yielded the tetrazolato complex [Pt(tpy)(N4CMe)](+), and solid state therm olysis resulted in decomposition. In order to examine the mode of binding o f the tetrazole to platinum, the related complex [Pt(tpy)(N4CPh)]BF4 was sy nthesized via a similar route. X-ray crystallography revealed that the tetr azolate ligand in this complex binds through the N 2 position. In addition, the gas-phase reactivity of these complexes has been investigated using el ectrospray-ionization tandem mass spectrometry (ESI-MS/MS). [Pt(tpy)N-3](+) fragments to form [Pt(tpy)N](+), which readily reacts with alcohols, CH3CN and (CH3)(2)CO, to form adducts. The [Pt(tpy)N+R'OH](+) adduct ions (R' = CH3, CH3CH2 and (CH3)(2)CH) fragment to yield [Pt(tpy)N+H-2](+) ions with c oncomitant oxidation of the alcohols.