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1. Brightly phosphorescent tetranuclear copper( i ) pyrazolates

   https://doi.org/10.1039/c9dt03402a  

   Dias, H. V.; Diyabalanage, Himashinie V.; Ghimire, Mukunda M.; Hudson, Joshua M.; Parasar, Devaborniny; Palehepitiya Gamage, Chammi S.; Li, Shan; Omary, Mohammad A. (October 2019, Dalton Transactions)

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   Described herein is the synthesis and photophysics of two tetranuclear copper complexes, {[3,5-(Pr i ) 2 ,4-(Br)Pz]Cu} 4 and {[3-(CF 3 ),5-(Bu t )Pz]Cu} 4 tailor-designed by manipulating the pyrazolyl ring substituents. Unlike their trinuclear analogues, the luminescence of the tetranuclear species is molecular (not supramolecular) in nature with extremely high solid-state quantum yields of ∼80% at room temperature. 

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2. Relativistic modulation of supramolecular halogen/copper interactions and phosphorescence in Cu( i ) pyrazolate cyclotrimers

   https://doi.org/10.1039/d2dt03725d  

   Lu, Zhou; Vanga, Mukundam; Li, Shan; Adebanjo, Joseph O.; Patterson, Monika R.; Dias, H. V.; Omary, Mohammad A. (March 2023, Dalton Transactions)

   Described herein are the synthesis, structure, and photophysics of the iodo-substituted cyclic trinuclear copper( i ) complex, Cu 3 [4-I-3,5-(CF 3 ) 2 Pz] 3 supported by a highly-fluorinated pyrazolate in comparison with its previously reported 4-Br/4-Cl analogues. The crystal structure is stabilised by multiple supramolecular interactions of Cu 3 ⋯I and hydrogen/halogen bonding. The photophysical properties and supramolecular interactions are investigated experimentally/computationally for all three 4-halo complexes vis-à-vis relativistic effects. 

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3. Coinage metal metallacycles involving a fluorinated 3,5-diarylpyrazolate

   https://doi.org/10.1039/d0nj03744c  

   Lakhi, Jaspreet S.; Patterson, Monika R.; Dias, H. V. (September 2020, New Journal of Chemistry)

   null (Ed.)

   Copper( i ) and silver( i ) pyrazolate complexes {[3,5-(3,5-(CF 3 ) 2 Ph) 2 Pz]Cu} 3 and {[3,5-(3,5-(CF 3 ) 2 Ph) 2 Pz]Ag} 3 have been synthesized using the fluorinated 3,5-(diaryl)pyrazole 3,5-(3,5-(CF 3 ) 2 Ph) 2 PzH and copper( i ) oxide and silver( i ) oxide, respectively. The gold( i ) analog was obtained from a reaction between Au(THT)Cl and [3,5-(3,5-(CF 3 ) 2 Ph) 2 Pz]H/NaH. The X-ray crystal structures show that the coinage metal complexes {[3,5-(3,5-(CF 3 ) 2 Ph) 2 Pz]M} 3 (M = Cu, Ag, Au) are trinuclear in the solid state. They feature distorted nine-membered M 3 N 6 metallacyclic cores. The M–N distances follow Cu < Au < Ag, which is the trend expected from covalent radii of the corresponding coinage metal ions. The 3,5-(3,5-(CF 3 ) 2 Ph) 2 PzH forms hydrogen bonded trimers in the solid state that are further organized by π-stacking between aryl rings. Solid samples of {[3,5-(3,5-(CF 3 ) 2 Ph) 2 Pz]M} 3 display blue photoluminescence. The copper complex {[3,5-(3,5-(CF 3 ) 2 Ph) 2 Pz]Cu} 3 is an excellent catalyst for mediating azide–alkyne cycloaddition chemistry. 

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4. Hydrogenation reactions catalyzed by HN(CH ₂ CH ₂ PR ₂ ) ₂ -ligated copper complexes

   https://doi.org/10.1039/d1qi00776a  

   Ekanayake, Dewmi A.; Chakraborty, Arundhoti; Krause, Jeanette A.; Guan, Hairong (October 2021, Inorganic Chemistry Frontiers)

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   HN(CH 2 CH 2 PR 2 ) 2 -ligated copper borohydride complexes, ( R PN H P)Cu(BH 4 ) (R = i Pr, Cy, t Bu), which can be prepared from ( R PN H P)CuBr and NaBH 4 , are capable of catalyzing the hydrogenation of aldehydes in an alcoholic solvent. More active hydrogenation catalysts are ( R PN H P)CuBr mixed with KO t Bu, allowing various aldehydes and ketones to be efficiently reduced to alcohols except those bearing a nitro, N -unprotected pyrrole, pyridine, or an ester group, or those prone to aldol condensation ( e.g. , 1-heptanal). Modifying the catalyst structure by replacing the NH group in ( i Pr PN H P)CuBr with an NMe group results in an inferior catalyst but preserves some catalytic activity. The hexanuclear copper hydride cluster, ( i Pr PN H P) 3 Cu 6 H 6 , is also competent in catalyzing the hydrogenation of aldehydes such as benzaldehyde and N -methyl-2-pyrrolecarboxaldehyde, albeit accompanied by decomposition pathways. The catalytic performance can be enhanced through the addition of a strong base or i Pr PN H P. The three catalytic systems likely share the same catalytically active species, which is proposed to be a mononuclear copper hydride ( R PN H P)CuH with the NH group bound to copper. 

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5. Copper( i ) and silver( i ) chemistry of vinyltrifluoroborate supported by a bis(pyrazolyl)methane ligand

   https://doi.org/10.1039/d1dt00974e  

   Zacharias, Adway O.; Mao, James X.; Nam, Kwangho; Dias, H. V. (June 2021, Dalton Transactions)

   null (Ed.)

   Although unsaturated organotrifluoroborates are common synthons in metal–organic chemistry, their transition metal complexes have received little attention. [CH 2 (3,5-(CH 3 ) 2 Pz) 2 ]Cu(CH 2 CHBF 3 ), (SIPr)Cu(MeCN)(CH 2 CHBF 3 ) and [CH 2 (3,5-(CH 3 ) 2 Pz) 2 ]Ag(CH 2 CHBF 3 ) represent rare, isolable molecules featuring a vinyltrifluoroborate ligand on coinage metals. The X-ray crystal structures show the presence of three-coordinate metal sites in these complexes. The vinyltrifluoroborate group binds asymmetrically to the metal site in [CH 2 (3,5-(CH 3 ) 2 Pz) 2 ]M(CH 2 CHBF 3 ) (M = Cu, Ag) with relatively closer M–C(H) 2 distances. The computed structures of [CH 2 (3,5-(CH 3 ) 2 Pz) 2 ]M(CH 2 CHBF 3 ) and M(CH 2 CHBF 3 ), however, have shorter M–C(H)BF 3 distances than M–C(H) 2 . These molecules feature various inter- or intra-molecular contacts involving fluorine of the BF 3 group, possibly affecting these M–C distances. The binding energies of [CH 2 CHBF 3 ] − to Cu + , Ag + and Au + have been calculated at the wB97XD/def2-TZVP level of theory, in the presence and absence of the supporting ligand CH 2 (3,5-(CH 3 ) 2 Pz) 2 . The calculation shows that Au + has the strongest binding to the [CH 2 CHBF 3 ] − ligand, followed by Cu + and Ag + , irrespective of the presence of the supporting ligand. However, in all three metals, the supporting ligand weakens the binding of olefin to the metal. The same trends were also found from the analysis of the σ-donation and π-backbonding interactions between the metal fragment and the π and π* orbitals of [CH 2 CHBF 3 ] − . 

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