A Bidentate Ligand Featuring Ditopic Lewis Acids in the Second Sphere for Selective Substrate Capture and Activation

We present a ligand platform featuring appended ditopic Lewis acids to facilitate capture/activation of diatomic substrates. We show that incorporation of two 9-borabicyclo[3.3.1]nonane (9-BBN) units on a single carbon tethered to a pyridine pyrazole scaffold maintains a set of unquenched nitrogen donors available to coordinate Fe^II, Zn^II, and Ni^II. Using hydride ion affinity and competition experiments, we establish an additive effect for ditopic secondary sphere boranes, compared to the monotopic analogue. These effects are exploited to achieve high selectivity for binding NO₂⁻ in the presence of competitive anions such as F⁻ and NO₃⁻. Finally, we demonstrate hydrazine capture within the second-sphere of metal complexes, followed by unique activation pathways to generate hydrazido and diazene ligands on Zn and Fe, respectively.     

Coordination Properties of Hydroxyisophthalic Acids: Topological Correlations,Synthesis, Structural Analysis,and Properties of New Complexes

Hydroxyisophthalic acids are valuable polytopic ligands for the design of functional materials based on coordination polymers due to the variety of charges and coordination modes they possess. Herein, we describe the synthesis, thermal stability, nonlinear optical (NLO) and spectroscopic properties of five novel coordination compounds, [K₂L(H₂O)₂], [MgL(H₂O)₂] ⋅ 3H₂O, [CaL(H₂O)₃], [SrL(H₂O)₃] ⋅ H₂O, [BaL(H₂O)(H₂O)₅], and one salt, (NH₄)₂L ⋅ 2H₂O, with 4,5,6-trihydroxyisophthalic acid (H₂L), which has not been tested in assembling crystalline coordination networks before. The peculiarities of the structural organization of the compounds were analyzed and compared with those for other hydroxyisophthalates. The coordination properties of hydroxyisophthalic acids were studied from the topological point of view, and a comparative topological analysis of coordination and H-bonded networks was performed. Structural correlations revealed in this study could be useful for the design of hydroxyisophthalate-based coordination networks, including porous metal-organic frameworks, proton conductors, and NLO materials.     

Iridium Complexes Containing Mesoionic C Donors: Selective C(sp3)H versus C(sp2)H Bond Activation,Reactivity Towards Acids and Bases,and Catalytic Oxidation of Silanes and Water

Metalation of a C2‐methylated pyridylimidazolium salt with [IrCp*Cl₂]₂ affords either an ylidic complex, resulting from C(sp³)?H bond activation of the C2‐bound CH₃ group if the metalation is performed in the presence of a base, such as AgO₂ or Na₂CO₃, or a mesoionic complex via cyclometalation and thermally induced heterocyclic C(sp²)?H bond activation, if the reaction is performed in the absence of a base. Similar cyclometalation and complex formation via C(sp²)?H bond activation is observed when the heterocyclic ligand precursor consists of the analogous pyridyltriazolium salt, that is, when the metal bonding at the C2 position is blocked by a nitrogen rather than a methyl substituent. Despite the strongly mesoionic character of both the imidazolylidene and the triazolylidene, the former reacts rapidly with D⁺ and undergoes isotope exchange at the heterocyclic C5 position, whereas the triazolylidene ligand is stable and only undergoes H/D exchange under basic conditions, where the imidazolylidene is essentially unreactive. The high stability of the Ir?C bond in aqueous solution over a broad pH range was exploited in catalytic water oxidation and silane oxidation. The catalytic hydrosilylation of ketones proceeds with turnover frequencies as high as 6 000 h^?1 with both the imidazolylidene and the triazolylidene system, whereas water oxidation is enhanced by the stronger donor properties of the imidazol‐4‐ylidene ligands and is more than three times faster than with the triazolylidene analogue.