Toward high nuclearity ruthenium complexes: creating new binding sites in metal complexes

Symmetric and Asymmetric Coupling of Pyridylpyrimidine for the Synthesis of Polynucleating Ligands

“…[3,4] Although dimetallic complex 2b was readily synthesised by an Ni-catalysed coupling of monometallic complex 1b, metal-free ligand 2a was required to fully interpret the electrochemical and spectroscopic properties of its complexes. Our initial attempt to synthesise 2a by the nickel-catalysed coupling of 1a failed to afford significant quantities of 2a (Scheme 1), presumably due to the sequestering of the nickel catalyst by the free chelating site in 1a or to its deactivation toward coupling as was previously shown for carbonylmetal compounds of chlorophenanthrolines.…”

Direct functionalization of the cyclometalated 2-(2′-pyridyl)phenyl ligand bound to iridium(III)

“…While functionalization of coordinated polypyridyl ligands have been well 0022-328X/$ -see front matter Ó 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.jorganchem.2005.03.013 explored [10], relatively few studies have been made on the ppy analogues [8,9]. Recent works on direct functionalization of ppy ligands bound to Ir(III) [8], Ru(II) [9], and Os(II) [11] suggest that functionalized Ir(III) cyclometalated complexes are easily available and can undergo further chemical transformations.…”

C–H Bond Functionalization of Arylpyrimidines Catalyzed by an in situ Generated Ruthenium(II) Carboxylate System and the Construction of Tris(heteroaryl)‐Substituted Benzenes

“…The use of multidentate pyrimidinecore ligands was demonstrated by Johansson et al in the preparation of high-nuclearity ruthenium complexes with interesting electronic properties. [14] As shown in Table 2, our arylation protocol, though less effective than with aryl bromides, proved to be applicable for the C-H functionalization of 1 with heteroaryl bromides. Accordingly, the reaction with 2-bromothiophene led to the disubstituted product 3j in a 68 % isolated yield, but the conversion of 1 was not complete after 18 h ( Table 2, Entry 10).…”