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Titolo:
Electrospray ionization tandem mass spectrometric studies competitive pyridine loss from platinum(II) ethylenediamine complexes by the kinetic method
Autore:
Holmes, RJ; OHair, RAJ; McFadyen, WD;
Indirizzi:
Univ Melbourne, Sch Chem, Melbourne, Vic 3010, Australia Univ Melbourne Melbourne Vic Australia 3010 elbourne, Vic 3010, Australia
Titolo Testata:
RAPID COMMUNICATIONS IN MASS SPECTROMETRY
fascicolo: 24, volume: 14, anno: 2000,
pagine: 2385 - 2392
SICI:
0951-4198(2000)14:24<2385:EITMSS>2.0.ZU;2-E
Fonte:
ISI
Lingua:
ENG
Soggetto:
GAS-PHASE; THERMOCHEMICAL DETERMINATIONS; AB-INITIO; AFFINITIES; CATIONS; IONS; CHEMISTRY; FRAGMENTATION; CISPLATIN; EXCHANGE;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
41
Recensione:
Indirizzi per estratti:
Indirizzo: O'Hair, RAJ Univ Melbourne, Sch Chem, Melbourne, Vic 3010, Australia Univ Melbourne Melbourne Vic Australia 3010 c 3010, Australia
Citazione:
R.J. Holmes et al., "Electrospray ionization tandem mass spectrometric studies competitive pyridine loss from platinum(II) ethylenediamine complexes by the kinetic method", RAP C MASS, 14(24), 2000, pp. 2385-2392

Abstract

The competition between pyridine ligand loss in square planar Pt(II) complexes has been examined using the doubly and singly charged ions of complexes consisting of platinum(ethylenediamine) coordinated to two different substituted pyridines, Collision induced dissociation (CID) of [Pt(en)Py1Py2](2) (where Py-1 = one of ten different substituted pyridines and Py-2 = pyridine) results in loss of the protonated pyridines to yield the singly charged platinum ions [Pt(en)Py-1-H](+) and [Pt(en)Py-2-H](+). In contrast, fragmentation of [Pt(en)Py1Py2-H](+) results in neutral pyridine loss to yield the ions [Pt(en)Py-1-H](+) and [Pt(en)Py-2-H](+). In the latter case, the correlation between relative losses of each pyridine compared to their gas-phase proton affinities is poor, A novel chloride ion abstraction reaction occurs for the fragmentation of [Pt(en)Py1Py2](2+) when Py-1 = o-C5H4CIN andPy-2 = C5H5N, to yield the [Pt(en)(Cl)Py-2](+) and [o-C5H4N](+) pair of ions, In order to model this process the competition between nitrogen and chlorine binding in [Pt(NH3)(3)(o-NC5H4Cl)](2+) has been examined using density functional theory (DFT) calculations at the B3LYP/ LANL2DZ level of theory, Both adducts are minima with the N adduct being more stable than the Cl adduct by 22.17 kcal mol(-1). Furthermore, the Cl adduct exhibits a significant stretching of the C-Cl bond (to 1.935 Angstrom), consistent with the observed chloride ion abstraction reaction, which is endothermic by 9.0 kcalmol(-1) (relative to the N adduct). Copyright (C) 2001 John Wiley & Sons, Ltd.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 09/07/20 alle ore 23:30:57