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• W2011275712 abstract "The site-differentiated, cyanide-substituted hexanuclear rhenium(III) selenide clusters cis- and trans-[Re6Se8(PEt3)4(CN)2] and [Re6Se8(PEt3)5(CN)]+ have been prepared from heterogeneous reactions of the corresponding iodo clusters with AgCN in refluxing chloroform. Isolated yields are 68%, 46%, and 64% for cis-[Re6Se8(PEt3)4(CN)2], trans-[Re6Se8(PEt3)4(CN)2], and [Re6Se8(PEt3)5(CN)]+, respectively. The new compounds are air- and water-stable and are characterized by X-ray diffraction crystallography, 31P NMR and IR spectroscopies, and FAB mass spectrometry. In related work, the solvent exchange rates of two site-differentiated monosolvate clusters, [Re6Se8(PEt3)5(MeCN)](SbF6)2 and [Re6Se8(PEt3)5(Me2SO)](SbF6)2, in neat solvents were measured by 1H NMR. These clusters are substitutionally inert; k ≈ 10-5−10-6 s-1 at 318 K. Activation parameters indicate a dissociative ligand exchange mechanism; ΔH⧧ values obtained from least-squares fitting of temperature-dependent kinetics data exceed RT by a factor of ca. 50 over the temperature range studied. These results demonstrate that the substitutional lability encountered in a previous study of cluster photophysics (Gray, T. G.; Rudzinski, C. M.; Nocera, D. G.; Holm, R. H. Inorg. Chem. 1999, 38, 5932) cannot result from ground-state thermal reactions." @default.
• W2011275712 created "2016-06-24" @default.
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• W2011275712 date "2002-06-29" @default.
• W2011275712 modified "2023-09-24" @default.
• W2011275712 title "Site-Differentiated Hexanuclear Rhenium(III) Cyanide Clusters [Re₆Se₈(PEt₃)<i>_n</i>(CN)₆_-<i>_n</i>]<i>ⁿ</i>^-⁴ (<i>n</i> = 4, 5) and Kinetics of Solvate Ligand Exchange on the Cubic [Re₆Se₈]²⁺ Core" @default.
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• W2011275712 doi "https://doi.org/10.1021/ic020214c" @default.
• W2011275712 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/12160409" @default.
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