Arene displacement, C-H activation and acetonitrile insertion reactions enabled by coordination of a functionalized iminophosphorane to a RuII-p-cymene scaffold.

Reaction of a sterically demanding iminophosphorano-phosphine, Ph2PCH2Ph2PNAr* (here onwards referred to as PCPNAr*; Ar* = 2,6-dibenzhydryl-4-methylphenyl), (1) with [Ru(η6-p-cymene)Cl2]2 yielded three different types of complex, [RuCl2{(η6-p-cymene)(PCPNAr*)-κ1-P}] (2), [RuCl{(P(O)CPNAr*)(κ2-N,C)(C-η6-arene)}] (3) and [RuCl{(POCPNAr*)(κ2-N,C-o)(C-η6-arene)}] (4), depending on the reaction conditions via CH activation, tethered η6-arene coordination, ortho-metallation or PN bond cleavage/rearrangement reactions. Interestingly, a similar reaction in CH3CN in the presence of AgBF4 resulted in the insertion of CH3CN into the PN bond to form a novel metallacycle [Ru(NCMe)3{(PC2PN(CH3)CNAr*)-κ3-N,N,P}][BF4]2 (5) containing 4- and 5-membered rings via an aza-Wittig type reaction. Complex 4 showed very good catalytic activity in the transfer hydrogenation of carbonyl compounds.

CuI-amidobis(phosphine) catalyzed C(sp3)-C(sp3) direct homo- and hetero-coupling of unactivated alkanes via C(sp3)-H activation.

Herein, we present a CuI-dimer, [CuI{Ph2PC6H4C(O)NC6H4PPh2-o}]2, which catalyzed direct C(sp3)-H homocoupling of benzyl and cycloalkane derivatives with excellent yields and regio-selectivity. The method is very simple and tolerates various functionalities. Synergistic metal-ligand cooperativity was observed in Cu-N bond cleavage and protonation of nitrogen, and facilitates a bifunctional pathway, minimising the free energy corrugation for catalytic intermediates.

Ferroelectric Behavior of an Octahedral Metal-Ligand Cage and Its 2D-Connected Cage Framework.

Supramolecular systems hold great potential as ferroelectric materials because they are easy to prepare and do not require toxic and environmentally damaging elements. However, directing the self-assembly process of a supramolecular array to yield polarizable solids is still challenging. Here, we describe induced ferroelectricity in a supramolecular framework of metal-organic cages that are supported by a flexible tripodal ligand (NHCH2 -(3-Py))3 PO (TPPA). Ferroelectric responses on the discrete cage [Cu6 (H2 O)12 (TPPA)8 ](NO3 )12 ⋅ 45H2 O (1) and its 2D-connected framework [{Cu6 Cl4 (H2 O)6 (TPPA)8 }(NO3 )8 ⋅ 60H2 O]n (2) yielded well-resolved rectangular hysteresis loops at room temperature with remnant polarization values of 27.27 and 29.09 µC/cm2 , respectively. Thermal hysteresis measurements (THM) and capacitance-voltage (C-V) plots further corroborate the ferroelectric behavior in these compounds. The polarization in them is due to the displacements of solvated molecules and nitrate ions in the pockets of these frameworks.