Metal-Mediated Synthesis of a Mixed Arduengo-Fischer Carbodicarbene Ligand.

Carbodicarbenes are strong C-donor ligands, which have found numerous applications in organometallic and main group element chemistry. Herein, we report a structurally distinct carbodicarbene ligand, which is formed by dinitrogenative coupling of a Fischer carbene complex with an N-heterocyclic diazoolefin. The resulting carbonyl complex serves as a stable source for the mixed Arduengo-Fischer carbodicarbene ligand. Facile ligand transfer reactions were demonstrated to occur with gold(I), copper(I), palladium(II), and rhodium(I) complexes.

Orientational Self-Sorting in Octahedral Palladium Cages: Scope and Limitations of the "cis Rule".

Octahedral coordination cages of the general formula [Pd6L12](BF4)12 were obtained by combining [Pd(CH3CN)4](BF4)2 with heteroditopic N-donor ligands. Four different ligands were employed. These ligands have 3-pyridyl donor groups at one end and 4-pyridyl, imidazolyl, or triazolyl donor groups at the other end. According to a geometric analysis, cages with a cis configuration at the six metal centers should be preferred ("cis rule"). This prediction was corroborated by spectroscopic data and crystallographic analyses. Limitations of the "cis rule" were also encountered, and possible explanations are discussed.

Two-Electron Redox Reactivity of Thorium Supported by Redox-Active Tripodal Frameworks.

The high stability of the + IVoxidation state limits thorium redox reactivity. Here we report the synthesis and the redox reactivity of two Th(IV) complexes supported by the arene-tethered tris(siloxide) tripodal ligands [(KOSiR2 Ar)3 -arene)]. The two-electron reduction of these Th(IV) complexes generates the doubly reduced [KTh((OSi(Ot Bu)2 Ar)3 -arene)(THF)2 ] (2OtBu ) and [K(2.2.2-cryptand)][Th((OSiPh2 Ar)3 -arene)(THF)2 ](2Ph -crypt) where the formal oxidation state of Th is +II. Structural and computational studies indicate that the reduction occurred at the arene anchor of the ligand. The robust tripodal frameworks store in the arene anchor two electrons that become available at the metal center for the two-electron reduction of a broad range of substrates (N2 O, COT, CHT, Ph2 N2 , Ph3 PS and O2 ) while retaining the ligand framework. This work shows that arene-tethered tris(siloxide) tripodal ligands allow implementation of two-electron redox chemistry at the thorium center while retaining the ligand framework unchanged.