OsH6(PiPr3)2 has been used to selectively activate C–H, O–H, and C–C sigma bonds in nucleobases and nucleosides, including derivatives of 6-phenylpurine and 4-phenylpyrimidine, leading to cyclometalated mononuclear Os–trihydride complexes, in excellent yields and as single products. Additionally, OsH6(PiPr3)2 promotes the efficient dehydrogenative decarbonylation of primary alcohols in nucleosides having unprotected sugar moieties. The incorporation of OsH2Cl2(PiPr3)2 in the structure of cyclometalated Ir­(III) and Rh­(III) half-sandwich complexes derived from nucleosides allows the preparation of a class of heterobimetallic bioorganometallic complexes having at least one M–C bond. These methodologies could be used in the future as a way for the orthogonal functionalization of oligonucleotides.

We report the preparation and the study of new types of neutral and cationic phosphorescent heteroleptic Ir(III) complexes derived from 6-phenylpurine nucleosides and nucleotides. Neutral complexes of general formula Ir(C^N)2(acac)...

The synthesis of a series of Pt{κ 3 -N,C,N′-[L]}X (X = Cl, RC�C) pincer complexes derived from purine and purine nucleosides is reported. In these complexes, the 6-phenylpurine skeleton provides the N,C-cyclometalated fragment, whereas an amine, imine, or pyridine substituent of the phenyl ring supplies the additional N′-coordination point to the pincer complex. The purine N,C-fragment has two coordination positions with the metal (N1 and N7), but the formation of the platinum complexes is totally regioselective. Coordination through the N7 position leads to the thermodynamically favored [6.5]-Pt{κ 3 -N7,C,N′-[L]}X complexes. However, the coordination through the N1 position is preferred by the amino derivatives, leading to the isomeric kinetic [5.5]-Pt{κ 3 -N1,C,N′-[L]}X complexes. Extension of the reported methodology to complexes having both pincer and acetylide ligands derived from nucleosides allows the preparation of novel heteroleptic bis-nucleoside compounds that could be regarded as organometallic models of Pt-induced interstrand cross-link. Complexes having amine or pyridine arms are green phosphorescence emitters upon photoexcitation at low concentrations in CH 2 Cl 2 solution and in poly(methyl methacrylate) (PMMA) films. They undergo self-quenching at high concentrations due to molecular aggregation. The presence of intermolecular π−π stacking and weak Pt•••Pt interactions was also observed in the solid state by X-ray diffraction analysis.