Pushing the limits of electron donation for -chelating ligands an alliance of phosphonium ylide and anionic abnormal NHC.

The grafting of a -(CH)PR moiety on an NHC ligand backbone in the Mn(I) complex [Cp(CO)Mn(IMes)] followed by double deprotonation opens a route to bidentate ligands with extreme electron-donating character. Such remarkable electronic properties can even allow intramolecular sp C-H functionalization in typically inert square-planar Rh(I) dicarbonyl complexes.

Combination of Phenylsilsesquioxane and Acetate Ligands as an Approach to a Record High Nuclear CuNa-Cage. Synthesis, Unique Structure, and Catalytic Activity.

Self-assembly synthesis of mixed-ligand (silsesquioxane/acetate) complex allows to isolate record high nuclear copper(II) Cu-cage (1). In the presence of two additional sodium ions, a unique molecular architecture, with triple combination of ligands (cyclic and acyclic silsesquioxanes as well as acetates), has been formed. The structure was established by single-crystal X-ray diffraction based on the use of synchrotron radiation.

An octanuclear 3-phenyl-5-(2-pyridyl)pyrazolate/phenylsilsesquioxane complex: synthesis, unique structure, and catalytic activity.

The first metallasilsesquioxane bearing pyrazolylpyridine ligands, the Cu-based complex 1, adopts a cage-like structure with two zigzag-type copper tetramers sandwiched by two cyclic Si silsesquioxane ligands. The four 3-phenyl-5-(2-pyridyl)pyrazolate ligands in 1 exhibit dual (chelating and bridging) modes of ligation. Compound 1 is very active in the oxidation of alkanes and alcohols.

Influence of triphosphine ligand coordination geometry in Mn(I) hydride complexes [(PPP)(CO)MnH] on their kinetic hydricity.

Octahedral Mn(I) complexes bearing tridentate donor ligands [(LL'L'')(CO)MnX] have recently emerged as major players in catalytic (de)hydrogenation processes. While most of these systems are still based on structurally rigid pincer scaffolds imposing a meridional coordination mode, for some more flexible tridentate ligands a facial arrangement of donor moieties becomes possible. Accordingly, the geometry of the corresponding Mn(I) hydrides [(LL'L'')(CO)MnH] directly involved in the catalytic processes, namely the nature of the donor extremity located in the -position of the hydride (CO and L for - and -configurations, respectively) may influence their hydride transfer ability.

Cu-Methylsilsesquioxane Cage Decorated with Cu(dppe) Moieties for Mild Oxidative Functionalization of Alkanes.

We report a high nuclear (Cu) complex synthesized via the self-assembly of copper-methylsilsesquioxane induced by the complexation with 1,2-bis(diphenylphosphino)ethane (dppe). The structure includes two cationic Cu(dppe) moieties and an anionic silsesquioxane cage of an unprecedented Cu structural type. The Cu cage fragment exhibits a unique () combination of Si-cyclic/Si-acyclic silsesquioxane ligands and () encapsulation of two different chloride and carbonate species.