75117-74-7Relevant academic research and scientific papers
Synthesis of the Cluster Dianion 2- by Pyrolysis and its Reactions with Electrophiles; X-Ray Structure Analysis of the Mixed-metal Derivative *CH2Cl2 and the Hydrido Derivative
Drake, Simon R.,Johnson, Brian F. G.,Lewis, Jack,Nelson, William W. J. H.,Vargas, Maria D.,et al.
, p. 1455 - 1464 (2007/10/02)
The new cluster species 2- (2) has been identified as one of the products resulting from the pyrolysis of .It reacts with BF4 to yield the monoanion - (4) and (5).The reaction of (2) with iodine-iodide produces as series of iodo-clusters - (8) and (9) which are converted back into (2) by addition of halide ions.The unstable monoanionic species - are obtained on reaction of (2) with +, and further reaction of (3) yields (6).The dianionic cluster (2) reacts with acid to give the monoanion - (10) and (11).The reaction with Hg(C6Cl5)(O2CCF3) yields initially the unstable monoanion - (12) which is rapidly converted into the known cluster dianion 2-.X-Ray analysis of the + salts of (4) and (10) reveal identical Os11 core geometries, but in (4) the copper ligand occupies a μ3-bridging position, while the hydride in (10) appears to be located in an interstitial site.
Redox chemistry of the cluster [Os10C(CO)24]2-
Drake, Simon R.,Barley, Mark H.,Johnson, Brian F. G.,Lewis, Jack
, p. 806 - 812 (2008/10/08)
The dianion [Os10C(CO)24]2- (1) is oxidized at a hanging drop mercury electrode (HDME) in a variety of media to produce [Os20(C)2(CO)48Hg2]2- (2), which on standing ultimately yields the known [Os20Hg(C)2(CO)48]2- (3). The dianion 1 is readily reduced electrochemically (at wave A in the cyclic voltammogram) by two electrons to yield the tetraanion [Os10C(CO)24]4- (5). This reduction was studied at a variety of electrodes and in different media and was found to be associated with an oxidation at more positive potentials (wave C). Electrochemical studies of 5 showed that 1 and 5 could be readily interconverted in close to 100% yield showing that the two redox processes were chemically reversible. From a comparison of the electrochemical and IR properties of 1 and 5 it was concluded that the two-electron reduction of 1 generated 5 with an associated minor change in structure, a process that was reversed upon oxidizing at wave C. When a solution of 1 is cooled, the two-electron wave (wave A) split into a quasi-reversible one-electron process and an irreversible wave which moved to more negative potentials as the temperature was reduced. The broad wave was linked to the oxidative feature (wave C) and demonstrated that the structural change occurs on the addition of the second electron to 1. The quasi-reversible electrochemical process was associated with the formation of the trianion [Os10C(CO)24]3- (4) which could be independently synthesized by the slow chemical reduction of 1. As suggested by the electrochemical results, samples of 4 disproportionated at room temperature and hence could not be further characterized. The species 2-5 have been prepared by independent chemical methods.
SYNTHESIS AND X-RAY ANALYSIS OF AND
Johnson, Brian F.G.,Lewis, Jack,Nelson, William J.H.,Vargas, Maria D.,Braga, Dario,at al.
, p. 2151 - 2162 (2007/10/02)
The cluster anion -(1) has been obtained from the reaction of in BuiOH and X-ray analysis of its + salt shows that the anion has an unusual fused tetrahedral metal-core geometry related to that of .Reaction of (1) with iodine gives (2) in which an overall change in cluster geometry has occurred; the reaction is reversible and heating (2) with iodide regenerates (1).Reaction of (1) with concentrated H2SO4 gives which reacts with P(OMe)3 to give > and with halide ions to give evantually 2-.Crystals of are triclinic, space group P, with a = 16.775(3), b = 13.509(2), c = 11.267(2) Angstroem, α = 89.88(1), β = 103.97(1), γ = 96.99(1)deg, and Z = 2.Refinement of atomic parameters using 5 615 absorption-corrected data converged at R = 0.0359.Crystals of *H2O are monoclinic, space group P21/c, with a = 14.386(2), b = 11.037(1), c = 24.629(3) Angstroem, β = 94.30(2)deg, and Z = 4.Refinement of atomic parameters using 4 644 absorptioncorrected reflections converged at R = 0.0569.
