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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. Full text not available from this repository. DOI: 10.1021/om051075k Abstractcis-[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).
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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]
