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The complexes [PtMedN-NjI {N-N = tbu2-bpy (4,4'-di-tert-butyl-2,2'-bipyridine), bpy (2,Y-bipyridine), or phen (1,lO-phenanthroline)} react with HX (X = C1, Br, I, 02CCF3, SO3CF3) to yield [PtXMe(N-N)l and CH4, by an oxidative addition lreductive elimination mechanism. The new alkyl(hydrido)platinum(N) intermediates [PtCUH)Medtbu2bpy)l (l), [PtBr(H)Medtbu2-bpy)] (2), [PtH(I)Medtbu2bpy)l ( 3 ) , and Pt(Cl(H.Me2-(bpy)], (a), formed by trans oxidative addition of HX, have been filly characterized at -78 "C by I H NMR spectroscopy. Rapid reductive elimination of CH4 ensues at higher temperatures to yield the corresponding organoplatinum(II) products [PtXMe(N-N)l. The thermal stability of the platinum(N) intermediates follows the sequence X = Cl ' Br > I > 02CCF3, SO3CF3.

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The first bifunctional Gd(III) complexes covalently bound to arylphosphonium cations and the first tumour-cell selective mitochondrial agents designed for potential application in binary cancer therapies are reported. The highest in vitro cellular uptake for any Gd complex reported to date is described, with levels exceeding 10(10) Gd atoms per tumour cell.

Cubane is a highly strained saturated hydrocarbon system that has historically been of interest in theoretical organic chemistry. More recently it has become a molecule of interest for biological applications due to its inherent stability and limited toxicity. Of greater significance is the ability to potentially functionalize cubane at each of its carbon atoms, providing complex biologically active molecules with unique spatial arrangements for probing active sites. These characteristics have led to an increased use of cubane in pharmaceutically relevant molecules. In this Perspective we describe synthetic methodology for accessing a range of functionalized cubanes and their applications in pharmaceuticals. We also provide some perspectives on challenges and future directions in the advancement of this field.

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Relative to other polycyclic frameworks (1−3), a carborane cage (4 and Cs·5) exerts a significant biological effect as an inhibitor of the purinergic P2X 7 receptor (P2X 7 R) which allows one to target depression in vivo and thus demonstrate, for the first time, that a carborane has the capacity to modify CNS activity.