The chemistry of the heterobinuclear platinum-iridium complex [PtIr(CO)3(μ-dppm)2][PF6], 1, dppm = Ph2PCH2PPh2, is described. The reaction of a hydride with 1 gave [HPtIr(CO)2(μ-dppm)2], by displacement of the carbonyl ligand from platinum, while reaction of 1 with dihydrogen, hydrogen chloride or Ph2MeSiH gave the fluxional complex [PtIrH4(CO)(μ-dppm)2][PF6], [PtIrH2Cl2(CO)(μ-dppm)2][PF6], or ...

The mixed donor tertiary phosphine {(Me(3)Si)(2)CH}P(C(6)H(4)-2-CH(2)NMe(2))(C(6)H(4)-2-CH(2)OMe) (11) is accessible via the stepwise addition of [Li(C(6)H(4)-2-CH(2)NMe(2))] followed by [Li(C(6)H(4)-2-CH(2)OMe)] to the dichlorophosphine {(Me(3)Si)(2)CH}PCl(2). Phosphine 11 is readily deprotonated by Bu(n)Li to give the lithium phosphinomethanide [[{(Me(3)Si)(2)C}P(C(6)H(4)-2-CH(2)NMe(2))(C(6)H...

The mercury (II) complex, Hg (Meca2en)I2 (1), containing bidentate Schiff base ligand  Meca2en = N,N′-bis[(E)-2-benzylidenepropylidene]ethane-1,2-diamine, has been synthesized and characterized by elemental analyses (CHN) and 1H-NMR spectroscopy. The crystal structure of 1 was determined using single-crystal X-ray diffraction. Structural investigation shows that 1 crystallizes in a monoclinic s...

The reaction of [(C5Me5)M(MeCN)3](PF6)2 with (C5Me5)2Ru2S4 gives the cluster compounds [(C5Me5)3MRu2S4(MeCN)](PF6)2, 1(PF6)2 (M ) Rh) and 3(PF6)2 (M ) Ir). Crystallographic studies of 1(PF6)2 show that the dication consists of an asymmetric RhRu2S4 core containing an isosceles triangle of metal atoms with a Ru-Ru bond of 2.88 Å. The three metal atoms are joined by two μ3-η:η:ηS2 units, each per...

The oxidation of the tribenzylphosphine derivative of the doubly cylcometallated platinum(II) complex of diphenylpyridine, 1, with PhICl2 led, as a first step, to the formation of a highly electrophilic metal centre which attacked the benzyl phosphine to give a triply cyclometallated species as the arenium ion. The highly acidic arenium ion protonated unreacted starting 1, a reaction that could...

The bis(imino)terpyridine ligands, 6,6''-{(2,6-i-Pr2C6H3)N=CR}2-2,2':6',2''-C15H9N3 (R = H L1, Me L2), have been prepared in high yield from the condensation reaction of the corresponding carbonyl compound with two equivalents of 2,6-diisopropylaniline. The molecular structure of L2 reveals a transoid relationship between the imino and pyridyl nitrogen groups throughout the ligand framework. Tr...

Size selection was demonstrated to suppress Ostwald ripening of supported catalytic nanoparticles. When the clusters are subnanometer in size and highly fluxional, such as Pt on rutile TiO2(110) surface, this paradigm breaks down, established theory sintering needs a revision. At temperatures characteristic catalysis (i.e. 700 K), sub-nano thermally populate many low-energy metastable isomers. ...

The electric dipole moments of (H2O)nDCl (n=3-9) clusters have been measured by the beam-deflection method. Reflecting the (dynamical) charge distribution within the system, the dipole moment contributes information about the microscopic structure of nanoscale solvation. The addition of a DCl molecule to a water cluster results in a strongly enhanced susceptibility. There is evidence for a noti...