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Titolo:
Kinetic and mechanistic aspects of sulfur recovery from Pd2I2(mu-S)(mu-dpm)(2) using I-2 and structures of Pd(II) complexes with the chelated monosulfide of dpm
Autore:
Wong, TYH; Rettig, SJ; James, BR;
Indirizzi:
Univ British Columbia, Dept Chem, Vancouver, BC V6T 1Z1, Canada Univ British Columbia Vancouver BC Canada V6T 1Z1 ver, BC V6T 1Z1, Canada
Titolo Testata:
INORGANIC CHEMISTRY
fascicolo: 9, volume: 38, anno: 1999,
pagine: 2143 - 2149
SICI:
0020-1669(19990503)38:9<2143:KAMAOS>2.0.ZU;2-X
Fonte:
ISI
Lingua:
ENG
Soggetto:
RAY CRYSTAL-STRUCTURE; MOLECULAR-STRUCTURES; MAGNETIC-RESONANCE; COORDINATION CHEMISTRY; HYDROGEN-SULFIDE; BIS(DIPHENYLPHOSPHINO)METHANE; LIGANDS; SE; CONVERSION; PALLADIUM;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
46
Recensione:
Indirizzi per estratti:
Indirizzo: James, BR Univnadatish Columbia, Dept Chem, 2036 Main Mall, Vancouver, BC V6T 1Z1, Ca Univ British Columbia 2036 Main Mall Vancouver BC Canada V6T 1Z1
Citazione:
T.Y.H. Wong et al., "Kinetic and mechanistic aspects of sulfur recovery from Pd2I2(mu-S)(mu-dpm)(2) using I-2 and structures of Pd(II) complexes with the chelated monosulfide of dpm", INORG CHEM, 38(9), 1999, pp. 2143-2149

Abstract

The Pd2X2(mu-S)(dpm)(2) complexes (2) (X = I, Br) react with halogens to yield PdX2(dpm) (3) and elemental sulfur. Kinetic and mechanistic studies onthe X = I system in CHCl3 reveal that the reaction proceeds via addition of I-2 to give Pd2I4(dpm)(2) (4c), which then undergoes unimolecular decomposition to generate PdI2(dpm) (3c); the liberated sulfur concatenates to form elemental Ss The addition reaction is in the stopped-flow time regime andis first-order in both 2c and I-2, with Delta H-double dagger = 32 +/- 1 kJ mol-l and Delta S-double dagger = -91 +/- 3 J K-1 mol(-1). The slower decomposition reaction of 4c is first order in 4c, with Delta H-double dagger.= 80 +/- kJ mol(-1) and Delta S-double dagger = -26 +/- 3 J K-1 mol(-1). Byproduct PdX2(dpm(S)) (5) [dpm(S) = Ph2PCH2P(S)Ph-2] also forms under some conditions via reaction of 3 with an S, species (n < 8). Complexes 5 (X = Cl (a), Br (b), I(c)) were also synthesized directly, and the structure of the 5c species, as well as of [Pd(dpm(S))(2)]Cl-2, were determined by X-ray analyses that reveal the envelope configuration of the five-membered Pd-PPh2CH2P(S)Ph-2 chelate ring.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 04/12/20 alle ore 12:30:26