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1. Stable abnormal N-heterocyclic carbenes and their applications

   https://doi.org/10.1039/c9cs00866G  

   Sau, Samaresh Chandra; Hota, Pradip Kumar; Mandal, Swadhin K.; Soleilhavoup, Michele; Bertrand, Guy (February 2020, Chemical Society Reviews)

   Although N-heterocyclic carbenes (NHCs) have been known as ligands for organometallic complexes since the 1960s, these carbenes did not attract considerable attention until Arduengo et al. reported the isolation of a metal-free imidazol-2-ylidene in 1991. In 2001 Crabtree et al. reported a few complexes featuring an NHC isomer, namely an imidazol-5-ylidene, also termed abnormal NHC (aNHCs). In 2009, it was shown that providing to protect the C-2 position of an imidazolium salt, the deprotonation occurred at the C-5 position, affording imidazol-5-ylidenes that could be isolated. Over the last ten years, stable aNHCs have been used for designing a range of catalysts employing Pd( ii ), Cu( i ), Ni( ii ), Fe(0), Zn( ii ), Ag( i ), and Au( i / iii ) metal based precursors. These catalysts were utilized for different organic transformations such as the Suzuki–Miyaura cross-coupling reaction, C–H bond activation, dehydrogenative coupling, Huisgen 1,3-dipolar cycloaddition (click reaction), hydroheteroarylation, hydrosilylation reaction and migratory insertion of carbenes. Main-group metal complexes were also synthesized, including K( i ), Al( iii ), Zn( ii ), Sn( ii ), Ge( ii ), and Si( ii / iv ). Among them, K( i ), Al( iii ), and Zn( ii ) complexes were used for the polymerization of caprolactone and rac -lactide at room temperature. In addition, based on the superior nucleophilicity of aNHCs, relative to that of their nNHCs isomers, they were used for small molecules activation, such as carbon dioxide (CO 2 ), nitrous oxide (N 2 O), tetrahydrofuran (THF), tetrahydrothiophene and 9-borabicyclo[3.3.1]nonane (9BBN). aNHCs have also been shown to be efficient metal-free catalysts for ring opening polymerization of different cyclic esters at room temperature; they are among the most active metal-free catalysts for ε-caprolactone polymerization. Recently, aNHCs successfully accomplished the metal-free catalytic formylation of amides using CO 2 and the catalytic reduction of carbon dioxide, including atmospheric CO 2 , into methanol, under ambient conditions. Although other transition metal complexes featuring aNHCs as ligand have been prepared and used in catalysis, this review article summarize the results obtained with the isolated aNHCs. 

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2. Insertion of CO ₂ Mediated by a (Xantphos)Ni ^I –Alkyl Species

   https://doi.org/10.1002/anie.201906005  

   Diccianni, Justin B.; Hu, Chunhua T.; Diao, Tianning (August 2019, Angewandte Chemie International Edition)

   Abstract The incorporation of CO₂into organometallic and organic molecules represents a sustainable way to prepare carboxylates. The mechanism of reductive carboxylation of alkyl halides has been proposed to proceed through the reduction of Ni^IIto Ni^Iby either Zn or Mn, followed by CO₂insertion into Ni^I‐alkyl species. No experimental evidence has been previously established to support the two proposed steps. Demonstrated herein is that the direct reduction of (tBu‐Xantphos)Ni^IIBr₂by Zn affords Ni^Ispecies. (tBu‐Xantphos)Ni^I‐Me and (tBu‐Xantphos)Ni^I‐Et complexes undergo fast insertion of CO₂at 22 °C. The substantially faster rate, relative to that of Ni^IIcomplexes, serves as the long‐sought‐after experimental support for the proposed mechanisms of Ni‐catalyzed carboxylation reactions. 

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3. Synthesis, characterization, and electrocatalytic activity of bis(pyridylimino)isoindoline Cu( ii ) and Ni( ii ) complexes

   https://doi.org/10.1039/D0DT03030A  

   Saha, Soumen; Sahil, Sha Tamanna; Mazumder, Md. Motiur; Stephens, Alexander M.; Cronin, Bryan; Duin, Evert C.; Jurss, Jonah W.; Farnum, Byron H. (January 2021, Dalton Transactions)

   null (Ed.)

   Two NNN pincer complexes of Cu( ii ) and Ni( ii ) with BPI Me − [BPI Me − = 1,3-bis((6-methylpyridin-2-yl)imino)isoindolin-2-ide] have been prepared and characterized structurally, spectroscopically, and electrochemically. The single crystal structures of the two complexes confirmed their distorted trigonal bipyramidal geometry attained by three equatorial N-atoms from the ligand and two axially positioned water molecules to give [Cu(BPI Me )(H 2 O) 2 ]ClO 4 and [Ni(BPI Me )(H 2 O) 2 ]ClO 4 . Electrochemical studies of Cu( ii ) and Ni( ii ) complexes have been performed in acetonitrile to identify metal-based and ligand-based redox activity. When subjected to a saturated CO 2 atmosphere, both complexes displayed catalytic activity for the reduction of CO 2 with the Cu( ii ) complex displaying higher activity than the Ni( ii ) analogue. However, both complexes were shown to decompose into catalytically active heterogeneous materials on the electrode surface over extended reductive electrolysis periods. Surface analysis of these materials using energy dispersive spectroscopy as well as their physical appearance suggests the reductive deposition of copper and nickel metal on the electrode surface. Electrocatalysis and decomposition are proposed to be triggered by ligand reduction, where complex stability is believed to be tied to fluxional ligand coordination in the reduced state. 

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4. Pyridine vs. Thiazole in Cyclometalated N^C^N Ni(II) Complexes

   https://doi.org/10.3390/inorganics13020041  

   Kletsch, Lukas; Jordan, Rose; Strippel, Julian; Vicic, David A; Klein, Axel (February 2025, Inorganics)

   Six N^C^N cyclometalated Ni(II) complexes [Ni(N^C^N)Cl] or [Ni(N^C^N’)Br] with symmetric N^C^N or non-symmetric N^C^N’ ligands in which the peripheral N-groups were varied with pyridine (Py), 4-thiazole (4Tz), 2-thiazole (2Tz), and 2-benzothiazole (2Btz) complementing the previously reported complexes with di(2-pyridyl)phenide ligands [Ni(Py(Ph)Py)X] X = Cl or Br. The non-symmetric [Ni(N^C^N’)Br] complexes were synthesized from NiBr2 and N^CH^N’ protoligands through base-assisted nickelation, while the symmetric [Ni(N^C^N)Cl] complexes were received from the N^C(Cl)^N protoligands and [Ni(COD)2] (COD = 1,5-cyclooctadiene). Introduction of 4Tz on both sides shifted the electrochemical gap ΔEexp = Eox–Ered and the long wavelength UV-vis absorption maxima of the complexes to higher energies, while 2Tz leads to a shift to lower energies. When introducing only one 4Tz or 2Tz as peripheral groups, the remaining PhPy moiety dominates the electronic properties and electrochemistry and photophysics are very similar to the Py(Ph)Py derivatives. In contrast to this, introduction of 2Btz shifts both values to lower energies, regardless of one or two 2Btz groups and the 2Btz moiety dominates the character of the frontier molecular orbitals of the complexes, as DFT calculations show. Long-wavelength UV-vis absorptions vary from 416 to 443 nm, and their energies correlate well with the first reduction potentials. Negishi-type C–C cross-coupling reactions gave total yields ranging from 1 to 60% and cross-coupling yields from 1 to 44%. The reactivities correlate roughly with the first reduction potentials. Facilitated reduction (E around –2 or higher) goes generally along with improved performance, making the thiazole-containing complexes interesting candidates for such catalysis. 

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5. Experimental and theoretical investigations of infrared multiple photon dissociation spectra of arginine complexes with Zn ²⁺ and Cd ²⁺

   https://doi.org/10.1039/c8cp03484b  

   Chalifoux, Aaron M.; Boles, Georgia C.; Berden, Giel; Oomens, Jos; Armentrout, P. B. (January 2018, Physical Chemistry Chemical Physics)

   Arginine (Arg) complexes with Zn 2+ and Cd 2+ were examined by infrared multiple photon dissociation (IRMPD) action spectroscopy using light from a free electron laser. Electrospray ionization generated complexes of deprotonated Arg with Zn 2+ , [Zn(Arg–H)] + , and Arg with CdCl + , CdCl + (Arg). Possible low-energy conformers of these species were found using quantum chemical calculations, and their calculated IR spectra were compared to experimentally measured IRMPD spectra. Calculations were performed at the B3LYP/6-311+G(d,p) level for Zn 2+ complexes and B3LYP/def2-TZVP with an SDD effective core potential on cadmium for CdCl + complexes. [Zn(Arg–H)] + was found to adopt a charge-solvated, tridentate [N,CO − ,N ω ′] structure where Zn 2+ binds to the backbone amine, carbonyl oxygen, and side-chain terminal guanidine nitrogen (N ω ′). The CdCl + (Arg) species was suggested to be a mixture of a dominant (∼85%) charge-solvated, tridentate [N,CO,N ω ′] structure where the CdCl + binds to the backbone amine, carbonyl, and side-chain imine (N ω ′) and a minor (∼15%) bidentate [N,CO − ](N ω ′H 2 + ) zwitterionic structure where the metal center binds to the backbone amine and carbonyl oxygen with intramolecular proton migration from the hydroxyl to the N ω ′ guanidine nitrogen (as designated in parenthesis). 

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