The first structurally characterised zerovalent platinum complex to contain a tridentate pincer-type coordination mode (κ3-SBS) is presented, raising further questions concerning the geometries and trans influence of Z-type ligands. © The Royal Society of Chemistry 2010.

The ensemble of forces that stabilize protein structure and facilitate biological function are intimately linked with the ubiquitous aqueous environment of living systems. As a consequence, biomolecular activity is highly sensitive to the interplay of solventĝ€"protein interactions, and deviation from the native conditions, for example by exposure to increased thermal energy or severe dehydration, results in denaturation and subsequent loss of function. Although certain enzymes can be extracted into non-aqueous solvents without significant loss of activity, there are no known examples of solvent-less (molten) liquids of functional metalloproteins. Here we describe the synthesis and properties of room-temperature solvent-free myoglobin liquids with near-native structure and reversible dioxygen binding ability equivalent to the haem protein under physiological conditions. The realization of room-temperature solvent-free myoglobin liquids with retained function presents novel challenges to existing theories on the role of solvent molecules in structural biology, and should offer new opportunities in protein-based nanoscience and bionanotechnology. © 2010 Macmillan Publishers Limited. All rights reserved.

The reaction of [Ru(η6-p-cymene)Cl2]2 with 2.0 mol equivalents of C(CH2SMe)4, C(CH 2SeMe)4, 1,2,4,5-C6H2(CH 2SMe)4 or 1,2,4,5-C6H2(CH 2SeMe)4 (L4) and [NH4][PF 6] in ethanol solution forms the [RuCl(η6-p-cymene) {κ2-L4}][PF6] complexes. Similar Os(II) complexes are obtained starting with [Os(η6-p-cymene)Cl 2]2. Treatment of [RuCl(η6-p-cymene) {κ2-L4}][PF6] with a further 0.5 mol equivalents of [Ru(η6-p-cymene)Cl2]2 or reaction of [Ru(η6-p-cymene)Cl2]2 directly with 1.0 mol equivalent of L4 forms the homobimetalllic [{RuCl(η6-p-cymene)}2{κ2κ ′2-L4}][PF6]2. Reaction of [OsCl(η6-p-cymene)-{κ2-C(CH2SeMe) 4}][PF6] with [Ru(η6-p-cymene)Cl 2]2 or [PtCl2(MeCN)2] affords the heterobimetallic [{OsCl(η6-p-cymene)}{RuCl(η6-p- cymene)}{κ2κ′2-C(CH2SeMe) 4}][PF6]2 and [{OsCl(η6-p- cymene)}{PtCl2}{κ2κ′2- C(CH2SeMe)4}][PF6] respectively. The complexes have been characterised by multinuclear NMR and IR spectroscopy and X-ray crystallography. The synthesis and properties of homomonometallic and homo-and hetero- bimetallic complexes based upon tetrathio-or tetraselenoether ligands with {(arene)MCl]+ units are described, and crystal structures reported for representative examples. © 2010 Elsevier B.V.