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Titolo:
Synthetic, structural, and solution thermochemical studies in the dimethylbis(phosphine)platinum(II) system. Dichotomy between structural and thermodynamic trends
Autore:
Haar, CM; Nolan, SP; Marshall, WJ; Moloy, KG; Prock, A; Giering, WP;
Indirizzi:
Univ New Orleans, Dept Chem, New Orleans, LA 70148 USA Univ New Orleans New Orleans LA USA 70148 Chem, New Orleans, LA 70148 USA Dupont Co, Cent Res & Dev, Expt Stn, Wilmington, DE 19880 USA Dupont Co Wilmington DE USA 19880 Dev, Expt Stn, Wilmington, DE 19880 USA Boston Univ, Dept Chem, Metcalf Ctr Sci & Engn, Boston, MA 02215 USA Boston Univ Boston MA USA 02215 calf Ctr Sci & Engn, Boston, MA 02215 USA
Titolo Testata:
ORGANOMETALLICS
fascicolo: 4, volume: 18, anno: 1999,
pagine: 474 - 479
SICI:
0276-7333(19990215)18:4<474:SSASTS>2.0.ZU;2-U
Fonte:
ISI
Lingua:
ENG
Soggetto:
N-PYRROLYL PHOSPHINES; PI-ACCEPTOR CHARACTER; LIGAND SUBSTITUTION; L(2)FE(CO)(3) SYSTEM; ENTHALPIES; COMPLEXES; CHEMISTRY;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
29
Recensione:
Indirizzi per estratti:
Indirizzo: Nolan, SP Univ New Orleans, Dept Chem, New Orleans, LA 70148 USA Univ New Orleans New Orleans LA USA 70148 Orleans, LA 70148 USA
Citazione:
C.M. Haar et al., "Synthetic, structural, and solution thermochemical studies in the dimethylbis(phosphine)platinum(II) system. Dichotomy between structural and thermodynamic trends", ORGANOMETAL, 18(4), 1999, pp. 474-479

Abstract

Reaction enthalpies of the complex (COD)PtMe2 (COD = eta(4)-1,5-cyclooctadiene) with an extensive series of unidentate phosphines have been measured by solution calorimetry. The molecular structures of cis-P2PtMe2 for P = PEt3, PMe2Ph, P(pyrrolyl)(3), and PCy3 have been determined by single-crystalX-ray diffraction. The relative stabilities of the resulting P-2-PtMe2 complexes are strongly influenced by the size (cone angle) of the incoming phosphine, with larger cone angles resulting in less thermodynamically stable complexes. Crystallographic and P-31 NMR data, however, do not reflect the enthalpic stability scale and are more closely correlated to the electronic(chi) character of the phosphine ligands. The strength of the Pt-P interaction, as determined from these structural data, is greatest for phosphines with electron-withdrawing substituents, regardless of phosphine size or reaction enthalpy.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 28/01/21 alle ore 06:51:42