Zucca, Antonio and Cordeschi, Diletta and Stoccoro, Sergio and Cinellu, Maria Agostina and Minghetti, Giovanni and Chelucci, Giorgio Adolfo and Manassero, Mario (2011) Platinum(II)-cyclometalated “roll-over” complexes with a chiral pinene-derived 2,2′-bipyridine. Organometallics, Vol. 30 (11), p. 3064-3074. eISSN 1520-6041. Article.
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The first nonracemic cyclometalated “roll-over” complex of platinum(II), [Pt(L-H)Me(DMSO)], has been synthesized in good yields by reaction of the chiral pinene-derived ligand (5S,7S)-5,7-methane-6,6-dimethyl-2-(pyridin-2-yl)-5,6,7,8-tetrahydroquinoline, L, with the electron-rich platinum complex [Pt(DMSO)2Me2]. Adducts have also been obtained, namely, [Pt(L)(Me)Cl] and [Pt(L)Cl2], when electron-poorer platinum complexes such as [Pt(DMSO)2(Me)Cl] or [Pt(DMSO)2Cl2] were used as reagents. The structure of [Pt(L)Cl2] has been solved by X-ray diffraction. Reaction of the mononuclear species [Pt(L-H)Me(DMSO)] with [Pt(Me)2(DMSO)2] under strictly controlled reaction conditions gives the dinuclear “double roll-over” complex [(DMSO)(Me)Pt(μ-L-2H)Pt(Me)-(DMSO)], in which the doubly deprotonated ligand L-2H acts as a bridging dianionic ligand with a four fused ring core. Protonation of the uncoordinated nitrogen ligand in [Pt(L-H)Me(DMSO)] gives the uncommon [Pt(L*)Me(DMSO)]+ cationic species, in which L* is the zwitterionic ligand originated from L-H by protonation of the uncoordinated nitrogen atom. Some aspects of the reactivity of the mononuclear roll-over species [Pt(L-H)Me(DMSO)] with acids and neutral ligands are also discussed.
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