Site-differentiated hexanuclear rhenium(III) cyanide clusters [Re(6)Se(8)(PEt(3))(n)()(CN)(6)(-)(n)()](n)()(-)(4) (n = 4, 5) and kinetics of solvate ligand exchange on the cubic [Re(6)Se(8)](2+) Core.
The site-differentiated, cyanide-substituted hexanuclear rhenium(III) selenide clusters cis- and trans-[Re(6)Se(8)(PEt(3))(4)(CN)(2)] and [Re(6)Se(8)(PEt(3))(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-[Re(6)Se(8)(PEt(3))(4)(CN)(2)], trans-[Re(6)Se(8)(PEt(3))(4)(CN)(2)], and [Re(6)Se(8)(PEt(3))(5)(CN)](+), respectively. The new compounds are air- and water-stable and are characterized by X-ray diffraction crystallography, (31)P NMR and IR spectroscopies, and FAB mass spectrometry. In related work, the solvent exchange rates of two site-differentiated monosolvate clusters, [Re(6)Se(8)(PEt(3))(5)(MeCN)](SbF(6))(2) and [Re(6)Se(8)(PEt(3))(5)(Me(2)SO)](SbF(6))(2), in neat solvents were measured by (1)H NMR. These clusters are substitutionally inert; k approximately 10(-)(5)-10(-)(6) s(-)(1) at 318 K. Activation parameters indicate a dissociative ligand exchange mechanism; DeltaH() 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.
Gray
Thomas G
TG
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
Holm
R H
RH