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1. Template-Free Synthesis of a Macrocyclic Bis(pyridine-dienamine) Proligand and Metal Complexes of Its Bis(pyridine-diimine) and Bis(pyridine-dienamido) Forms

   https://doi.org/10.1021/acs.inorgchem.9b02539  

   Reinhart, Erik D.; Jordan, Richard F. (November 2019, Inorganic Chemistry)
2. 2,6-Bis[bis(1,1-dimethylethyl)phosphinito-κP]phenyl-κC]-trans-chlorohydro(phenylphosphine)iridium(III)

   https://doi.org/10.3390/M1388  

   Mucha, Neil T.; Waterman, Rory (June 2022, Molbank)

   The molecular structure of an iridium complex featuring a phenylphosphine ligand is described. The reaction of (POCOP)IrHCl (1, POCOP = 2,6-(tBu2PO)2C6H3–) with phenylphosphine gives (POCOP)IrHCl(PH2Ph) (2) under mild conditions. The structural features are consistent with a classic pseudo-octahedral iridium compound with three neutral phosphine donors. Compound 1 is unreactive at elevated temperatures and is unreactive toward excess phenylphosphine under the sampled conditions. 

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3. Nickel-Templated Replacement of Phosphine Substituents in a Tetradentate Bis(amido)bis(phosphine) Ligand

   https://doi.org/10.1021/acs.inorgchem.1c02750  

   Lee, Kyounghoon; Thomas, Christine M. (November 2021, Inorganic Chemistry)
4. Cationic Bis(Gold) Indenyl Complexes

   https://doi.org/10.1002/cplu.202300691  

   Slinger, Brady_L; Zhu, Jiaqi; Widenhoefer, Ross_A (February 2024, ChemPlusChem)

   Abstract Reaction of (P)AuOTf [P=P(t‐Bu)₂o‐biphenyl] with indenyl‐ or 3‐methylindenyl lithium led to isolation of gold η¹‐indenyl complexes (P)Au(η¹‐inden‐1‐yl) (1 a) and (P)Au(η¹‐3‐methylinden‐1‐yl) (1 b), respectively, in >65 % yield. Whereas complex1 bis static, complex1 aundergoes facile, degenerate 1,3‐migration of gold about the indenyl ligand (ΔG^≠_153K=9.1±1.1 kcal/mol). Treatment of complexes1 aand1 bwith (P)AuNTf₂led to formation of the corresponding cationic bis(gold) indenyl complexestrans‐[(P)Au]₂(η¹,η¹‐inden‐1,3‐yl) (2 a) andtrans‐[(P)Au]₂(η¹,η²‐3‐methylinden‐1‐yl) (2 b), respectively, which were characterized spectroscopically and modeled computationally. Despite the absence of aurophilic stabilization in complexes2 aand2 b, the binding affinity of mono(gold) complex1 atoward exogenous (P)Au⁺exceed that of free indene by ~350‐fold and similarly the binding affinity of1 btoward exogenous (P)Au⁺exceed that of 3‐methylindene by ~50‐fold. The energy barrier for protodeauration of bis(gold) indenyl complex2 awith HOAc was ≥8 kcal/mol higher than for protodeauration of mono(gold) complex1 a. 

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5. Bis-arylation of phenylene-bridged bis-azolium salts and tetra-arylation of bis-azoles to access symmetrical and unsymmetrical CCC-aNHC pincer ligand precursors

   https://doi.org/10.1016/j.tet.2025.135045  

   Cecil, AC; Fosu, E; Donnadieu, B; Hollis, TK (January 2026, Tetrahedron)

   Copper-mediated methodologies for the arylation of bis-azolium salts and bis-azoles are efficient pathways to access symmetrical and unsymmetrical N-heterocyclic carbene precursors. The arylation of bis-azolium salts with various aryl halides was achieved in moderate yields to furnish numerous C2-arylated bis-azolium salts. Access of C2-arylated bis-azolium salts from bis-azoles was also achieved in a single pot domino reaction via the use of iodonium salts as embedded electrophiles. The latter methodology utilizes the aryl iodide byproduct from the N-arylation step for the C–H activation step to mitigate waste and the need to recycle. We also demonstrated the use of these azolium salts in metalation and found success in obtaining metal complexes containing abnormal N-heterocyclic carbenes. 

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