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Dinuclear C,N,C cyclometalated platinum derivatives with bridging delocalized ligands: fourfold deprotonation of 6,6‘-diphenyl-2,2‘-bipyridine, H4L, promoted by “Pt(R)2” fragments (R = Me, Ph): crystal structures of [Pt2(L)(3,5-Me2py)2] and {Pt2(L)(dppe)}2 (dppe = 1,2-bis(diphenylphosphino)ethane): X-ray powder diffraction of [Pt2(L)(CO)2]

Zucca, Antonio and Petretto, Giacomo Luigi and Stoccoro, Sergio and Cinellu, Maria Agostina and Minghetti, Giovanni and Manassero, Mario and Manassero, Carlo and Male, Louise and Albinati, Alberto (2006) Dinuclear C,N,C cyclometalated platinum derivatives with bridging delocalized ligands: fourfold deprotonation of 6,6‘-diphenyl-2,2‘-bipyridine, H4L, promoted by “Pt(R)2” fragments (R = Me, Ph): crystal structures of [Pt2(L)(3,5-Me2py)2] and {Pt2(L)(dppe)}2 (dppe = 1,2-bis(diphenylphosphino)ethane): X-ray powder diffraction of [Pt2(L)(CO)2]. Organometallics, Vol. 25 (9), p. 2253-2265. eISSN 1520-6041. Article.

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DOI: 10.1021/om051075k

Abstract

cis-[Pt(R)2(DMSO)2] (R = Me, Ph) reacts with 6,6‘-diphenyl-2,2‘-bipyridine (H4L) in a 2:1 molar ratio, giving the unusual, very slightly soluble dinuclear complex [Pt2(L)(DMSO)2] (1). The reaction implies activation of four C−H bonds: in 1 a fourfold deprotonated H4L links two Pt−DMSO fragments acting as a delocalized C,N,C^C,N,C 12-electron donor. From 1 more soluble dinuclear [Pt2(L)(L‘)2] (L‘ = bulky 2-electron donors such asPR3 and substituted pyridines) species, 2−6, and polynuclear {Pt2(L)(L−L)}n (L−L = Ph2P(CH2)xPPh2 (x = 1, dppm; x = 2, dppe; x = 3, dppp)) species, 7−9, have been obtained by substitution of the DMSO ligands. DMSO can also be displaced from 1 by CO, both in solution and in the solid state, to give the flat and completely insoluble complex [Pt2(L)(CO)2] (10). The structures of [Pt2(L)(3,5-Me2-Py)2] (5) and {Pt2(L)(dppe)}2 (8) have been determined by single-crystal X-ray diffraction analysis, while a powder X-ray diffraction analysis has been performed on complex 10, [Pt2(L)(CO)2]. With a 1:1 Pt:L molar ratio a mononuclear complex, [Pt(H2L)(DMSO)] (11), is obtained, where the twofold deprotonated ligand is C,N,C coordinated. Also, the DMSO can be displaced from 11 by neutral ligands, L‘, such as CO, PPh3, and 3,5-Me2-py to give [Pt(H2L)(L‘)] (12−14). Compounds 11−14 further react with cis-[Pt(R)2(DMSO)2] to give dinuclear complexes. This two-step approach allows us to obtain species with different ligands around each platinum atom, [Pt2(L)(L‘)(L‘ ‘)] (15−18).

Item Type:Article
ID Code:4034
Status:Published
Refereed:Yes
Uncontrolled Keywords:Cyclometalated compounds, crystal structures, x-ray powder diffraction
Subjects:Area 03 - Scienze chimiche > CHIM/03 Chimica generale e inorganica
Divisions:001 Università di Sassari > 01 Dipartimenti > Chimica
Publisher:American Chemical Society
eISSN:1520-6041
Deposited On:17 Jun 2010 13:20

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