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Metallation of unactivated methyl groups: platinum(II) derivatives with 6-alkyl-2,2′-bipyridines

Zucca, Antonio and Stoccoro, Sergio and Cinellu, Maria Agostina and Minghetti, Giovanni and Manassero, Mario and Sansoni, Mirella (2002) Metallation of unactivated methyl groups: platinum(II) derivatives with 6-alkyl-2,2′-bipyridines. European Journal of Inorganic Chemistry, Vol. 2002 (12), p. 3336-3346. eISSN 1099-0682. Article.

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DOI: 10.1002/1099-0682(200212)2002:12<3336::AID-EJIC3336>3.0.CO;2-Z


The reaction of K2[PtCl4] with three 6-alkyl-2,2′-bipyridines HL, (N2C10H7R; R = CH2Me, HLet; CHMe2, HLip; CH2CMe3, HLnp) affords five- and six-membered cyclometallated complexes [Pt(L)Cl] where L is a terdentate N,N,C anionic ligand which originates from HL through direct activation of a C(sp3)−H bond. In the case of HLip, metallation generates a stereogenic carbon atom β to the metal. Complex 5, [Pt(Lnp)Cl], having an uncommon six-membered ring containing a Pt−C(sp3) bond, was studied in depth in solution, by means of 1- and 2- dimensional NMR spectroscopy, and in the solid state by X-ray diffraction. Differences are observed in the behaviour of these ligands: thus with HLet an adduct, [Pt(HLet)Cl2], was also isolated and its structure was determined by X-ray diffraction. In the metallated species, the fourth ligand, Cl, can easily be substituted by neutral or anionic ligands (CO, PPh3, CN). The metallated species react with potentially bidentate ligands L′−L′′ [Ph2PCH2PPh2 (dppm), Ph2P(CH2)2PPh2 (dppe), Ph2P(CH2)2AsPh2 (dppae)] to give, with different Pt:L ratios, mononuclear [Pt(L)(L′−L′′)]+ or dinuclear [(L)Pt(μ−L′−L′′)Pt(L)]++ cationic species. In the second case an uncommon unsupported L′−L′′ bridge is present. The cyclometallated species are stable in air and moisture, and the N,N,C system is rather robust.

Item Type:Article
ID Code:5332
Uncontrolled Keywords:Platinum, N ligands, cyclometallation
Subjects:Area 03 - Scienze chimiche > CHIM/03 Chimica generale e inorganica
Divisions:001 Università di Sassari > 01 Dipartimenti > Chimica
Deposited On:27 Jan 2011 10:15

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