Complexes of the tripodal phosphine ligands PhSi(XPPh2)3 (X = CH2, O): synthesis, structure and catalytic activity in the hydroboration of CO2.

The coordination chemistry of Fe(2+), Co(2+) and Cu(+) ions was explored with the triphosphine and triphosphinite ligands PhSi{CH2PPh2}3 (1) and PhSi{OPPh2}3 (2), so as to evaluate the impact of the electronic properties of the tripodal phosphorus ligands on the structure and reactivity of the corresponding complexes. The synthesis and characterization of the complexes [Fe(κ(3)-PhSi{CH2PPh2}3)(MeCN)3][OTf]2 (3) (OTf = O3SCF3), [Fe(κ(3)-PhSi{OPPh2}3)(MeCN)3][OTf]2 (3'), [Co(κ(2)-PhSi{CH2PPh2}3)Cl2] (4), [Co(κ(3)-PhSi{OPPh2}3)Cl2] (4'), [Cu(κ(3)-PhSi{CH2PPh2}3)Br] (5) and [Cu(κ(3)-PhSi{OPPh2}3)I] (5') were carried out. The crystal structures of 3, 3', 4, 4', and of the solvates 5·3THF and 5'·THF are reported.

Efficient disproportionation of formic acid to methanol using molecular ruthenium catalysts.

The disproportionation of formic acid to methanol was unveiled in 2013 using iridium catalysts. Although attractive, this transformation suffers from very low yields; methanol was produced in less than 2% yield, because the competitive dehydrogenation of formic acid (to CO2 and H2) is favored. We report herein the efficient and selective conversion of HCOOH to methanol in 50% yield, utilizing ruthenium(II) phosphine complexes under mild conditions.

Vapour pressure dependence and thermodynamics of cylindrical metal-organic framework mesoparticles: an ESEM study.

Self-assembly of neodymium nitrate and 2,5-dihydroxyl-1,4-benzoquinone (DHBQ) leads to the formation of a metal organic framework (MOF) of formula [Nd2(DHBQ)3(H2O)6]·18H2O. X-ray diffraction studies show that its crystalline structure is that of a two-dimensional coordination polymer packed in parallel sheets, with organised clusters of water molecules lying between the sheets and bridging them via a dense H-bond network. However, instead of forming faceted crystals, this MOF assembles into unusually shaped cylindrical particles of micrometre size.

Interaction of thioether groups at the open coordination sites of palladium(II) and platinum(II) complexes probed by luminescence spectroscopy at variable pressure.

The crystal structures of [PtCl(2)(ttcn)], [PdCl(2)(ttcn)], [Pt(ethylenediamine)(ttcn)](PF(6))(2), and [Pd(ethylenediamine)(ttcn)](PF(6))(2) (ttcn = 1,4,7-trithiacyclononane) show short apical metal---S(ttcn) distances, qualitatively indicating an interaction. Luminescence spectroscopy was used to study these crystalline complexes at room temperature and variable hydrostatic pressure. The luminescence band maximum of [PdCl(2)(ttcn)] shows a pressure-induced blue shift of +6 cm(-1)/kbar, while the platinum(II) compounds show a red shift of approximately -20 cm(-1)/kbar.