CH 3 ) 2 Pt(µ-SMe 2 )] 2 catalyzes the formation of aryl methyl ethers Via selectiVe C-F bond actiVation of polyfluoroarylimines. This reaction is functional group tolerant and proceeds in good to excellent yields. The optimization and preliminary substrate scope of this process are described.The activation of strong carbon-element bonds remains a significant challenge in organometallic chemistry. In recent years, platinum-based complexes have shown increasing potential for selective carbon-atom bond activation. Detailed mechanistic investigations of these transformations have brought new understanding to the range of reactivity accessible. Significant advances in platinum chemistry include carbon-hydrogen 1 and carbon-halogen bond activation, 2 complexes of heavier element species, 3 reductive elimination from both Pt(II) 4 and Pt(IV) species, 5 dehydrogenation, 6 and a range of applications such as sensors for SO 2 and other gases, 7 biosensors, 8 and photochemical products. 9 Moreover, the use of Pt(II)/Pt(IV) redox cycles in catalysis is becoming increasingly common. In particular, we have been interested in using Pt(II) complexes to catalyze the activation and subsequent functionalization of aryl C-F bonds. Although several examples of stoichiometric 1a,r,2b,10 and catalytic C-F activation have been reported, 11 only limited examples for the catalytic cross-coupling of polyfluoroarenes have emerged. 12 We recently reported that [(CH 3 ) 2 Pt(µ-SMe 2 )] 2 catalyzes the methylation of a wide range of fluorinated aryl Crespo, M.; Granell, J.; Vizcarro, A.; Zafrilla, J.; Font-Bardia, M.; Solans, X. Albrecht, M.; Lutz, M.; Schreurs, A. M. M.; Lutz, E. T. H.; Spek, A. L.; van Koten, G. Dalton Trans. 2000, 3797-3804. (c) Albrecht, M.; Lutz, M.; Spek, A. L.; van Koten, G. Nature (London) 2000, 406, 970-974. (d) Albrecht, M.; Gossage, R. A.; Lutz, M.; Spek, A. L.; van Koten, G.

The first examples of actinide complexes incorporating corrole ligands are presented. Thorium(IV) and uranium(IV) macrocycles of Mes2(p-OMePh)corrole were synthesized via salt metathesis with the corresponding lithium corrole in remarkably high yields (93% and 83%, respectively). Characterization by single-crystal X-ray diffraction revealed both complexes to be dimeric, having two metal centers bridged via bis(μ-chlorido) linkages. In each case, the corrole ring showed a large distortion from planarity, with the Th(IV) and U(IV) ions residing unusually far (1.403 and 1.330 Å, respectively) from the N4 plane of the ligand. (1)H NMR spectroscopy of both the Th and U dimers revealed dynamic solution behavior. In the case of the diamagnetic thorium corrole, variable-temperature, DOSY (diffusion-ordered) and EXSY (exhange) (1)H NMR spectroscopy was employed and supported that this behavior was due to an intrinsic pseudorotational mode of the corrole ring about the M-M axis. Additionally, the electronic structure of the actinide corroles was assessed using UV-vis spectroscopy, cyclic voltammetry, and variable-temperature magnetic susceptibility. This novel class of macrocyclic complexes provides a rich platform in an underdeveloped area for the study of nonaqueous actinide bonding and reactivity.

We recently discovered that Wilkinson's catalyst (ClRh(PPh3)3) is an excellent catalyst for alkyne hydrothiolation with alkanethiols to provide linear alkyl (E)-vinyl sulfides, which are valuable synthetic intermediates and precursors to bioactive molecules. Deuterium-labeling studies indicate that the reaction proceeds by thiol oxidative addition, alkyne migratory insertion, and subsequent reductive elimination.

The first examples of lanthanide corroles are prepared by two synthetic routes. (Mes2(p-OMePh)corrole)La·4.5DME (1·4.5DME) and (Mes2(p-OMePh)corrole)Tb·4DME (2·4DME) are prepared from the free base corrole and Ln((NSiMe3)2)3, while (Mes2(p-OMePh)corrole)Gd·TACNMe3 (3·TACNMe3) is prepared by metathesis of the recently reported Li3 corrole and GdCl3.

A readily accessible, user-friendly Pt(II) complex (Cl2Pt(SMe2)2, 2) shows good reactivity for selective, catalytic methylation of polyfluoroarylimines.