Dalton Transactions

doi: 10.1039/c5dt90212fpmid: N/A

doi: 10.1039/C5DT90212Fpmid: N/A

doi: 10.1039/C5DT90213Dpmid: N/A

doi: 10.1039/c5dt90213dpmid: N/A

doi: 10.1039/C5DT90214Bpmid: N/A

doi: 10.1039/c5dt90214bpmid: N/A

Safin, Damir A.; Frost, Jamie M.; Murugesu, Muralee

doi: 10.1039/c5dt03435cpmid: 26503295

In this perspective we report on recently accumulated data on the synthesis and coordination chemistry of 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (TPymT). Although a highly attractive ligand, owing to the presence of three fused terpyridine-like coordination pockets, the coordination chemistry of TPymT has something of a chequered past. This can principally be attributed to the hydrolysis of the ligand, which readily occurs under mild conditions. Thus, after first being synthesised in 1959 it had only been used a handful of times to synthesise coordination compounds until we began reinvestigating its chemistry in early 2013. Despite the significant challenges associated with its use, our work over the past two years has demonstrated that coordination chemistry with TPymT is indeed possible. Herein, we describe an overview of this body of work as it stands, and discuss its potential impact in a variety of areas including porous materials, catalysis and crystal engineering.

Caballero, Ana; Díaz-Requejo, M. Mar; Fructos, Manuel R.; Olmos, Andrea; Urbano, Juan; Pérez, Pedro J.

doi: 10.1039/c5dt03450gpmid: 26568268

The direct functionalization of low reactive C(sp3)–H and C(sp2)–H bonds of alkanes and arenes, respectively, by metal-induced carbene transfer from diazo compounds is reviewed. To date, this methodology has enabled the incorporation of CR1R2 moieties from N2CR1R2 in a chemo, regio, enantio or diastereoselective manner in those substrates with the appropriate selection of metal and ligands.

Pitto-Barry, Anaïs; Perdigao, Luis M. A.; Walker, Marc; Lawrence, James; Costantini, Giovanni; Sadler, Peter J.; Barry, Nicolas P. E.

doi: 10.1039/c5dt03205apmid: 26418726

We have synthesised osmium nanoparticles of defined size (1.5–50 nm) on a B- and S-doped turbostratic graphitic structure by electron-beam irradiation of an organometallic osmium complex encapsulated in self-spreading polymer micelles, and characterised them by transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and atomic force microscopy (AFM) on the same grid. Oxidation of the osmium nanoparticles after exposure to air was detected by X-ray photoelectron spectroscopy (XPS).

Materna, Kelly L.; Brennan, Bradley J.; Brudvig, Gary W.

doi: 10.1039/c5dt03463apmid: 26506505

A ruthenium complex containing silatrane functional groups has been synthesized and covalently bound to a conductive metal oxide film composed of nanoparticulate ITO (nanoITO). The silatrane-derived siloxane surface anchors were found to be stable in the examined range of pH 2 to 11 in aqueous phosphate buffer, and the ruthenium complex was found to have stable electrochemical features with repeated electrochemical cycling. The non-coordinating properties of the silatrane group to metals, which facilitates synthesis of silatrane-labeled coordination complexes, together with the facile surface-binding procedure, robustness of the surface linkages, and stability of the electrochemical properties suggest that incorporating silatrane motifs into ligands for inorganic complexes provides superior properties for attachment of catalysts to metal oxide surfaces under aqueous conditions.