Reversible Electrochemical Lithium-Ion Insertion into the Rhenium Cluster Chalcogenide-Halide ReSeCl.

The cluster-based material ReSeCl is a two-dimensional ternary material with cluster-cluster bonding across the a and b axes capable of multiple electron transfer accompanied by ion insertion across the c axis. The Li/ReSeCl system showed reversible electron transfer from 1 to 3 electron equivalents (ee) at high current densities (88 mA/g). Upon cycling to 4 ee, there was evidence of capacity degradation over 50 cycles associated with the formation of an organic solid-electrolyte interface (between 1.

Small molecule activation of nitriles coordinated to the [ReSe] core: formation of oxazine, oxazoline and carboxamide complexes.

Novel oxazine, oxazoline and carboxamide cluster complexes were prepared when different nucleophilic oxygen species reacted with nitriles coordinated to the Lewis acidic [Re6Se8]2+ cluster core. Reaction of ICH2CH2O- (generated in situ) with [Re6Se8(PEt3)5(NCR)]A2 (1A2 (R = Me) and 2A2 (R = Ph) where A = BF4-), leads to the formation of [Re6Se8(PEt3)5(2-methyloxazoline)]2+ (32+) and [Re6Se8(PEt3)5(2-phenyloxazoline)]2+ (42+). Similarly, reaction of BrCH2CH2CH2O- with the same nitrile complexes, 1A2 and 2A2 (where A = BF4- or SbF6-) leads to the corresponding oxazine complexes, [Re6Se8(PEt3)5(2-methyloxazine)]2+ (52+) and [Re6Se8(PEt3)5(2-phenyloxazine)]2+ (62+).

Crystal structure of octa-μ3-selenido-(p-toluene-sulfonato-κO)penta-kis-(tri-ethyl-phosphane-κP)-octa-hedro-hexa-rhenium(III) p-toluene-sulfonate di-chloro-methane disolvate.

The title compound, [Re6Se8{O3SC6H4(CH3)}{P(C2H5)3}5](CH3C6H4SO3)·2CH2Cl2, contains the face-capped hexa-nuclear [Re6(μ3-Se)8](2+) cluster core. The [Re6Se8](2+) cluster core displays a non-crystallographic center of symmetry and is bonded through the Re(III) atoms to five tri-ethyl-phosphane ligands and one p-toluene-sulfonate ligand. One p-toluene-sulfonate counter-ion and two di-chloro-methane solvent mol-ecules are also present in the asymmetric unit.

Organometallic rhenium(III) chalcogenide clusters: coordination of N-heterocyclic carbenes.

The preparation of rhenium based octahedral clusters containing N-heterocyclic carbenes is described. These represent the first examples of [M6(μ3-Q)8](n+) or [M6(μ3-X)8](n+) clusters to contain a carbene ligand of any type (NHC, Fischer or Schrock). Surprisingly, the NHC ligands attenuate their luminescent properties.

Octa-μ3-selenido-penta-kis-(tri-ethyl-phos-phane-κP)(tri-methyl-aceto-nitrile-κN)-octa-hedro-hexa-rhenium(III) bis-(hexa-fluorido-anti-monate) tri-methyl-aceto-nitrile monosolvate.

The crystal structure of the title compound, [Re6Se8{NCC(CH3)3}(Et3P)5](SbF6)2·NCC(CH3)3, contains a face-capped octa-hedral [Re6(μ3-Se)8](2+) cluster core. The pseudo-centrosymmetric [Re6Se8](2+) cluster core is bonded through the Re atoms to five tri-ethyl-phosphane ligands and one tri-methyl-aceto-nitrile ligand. No significant interactions are observed between the cationic cluster, the SbF6 (-) anions and the trimethylacetonitrile solvent molecule.