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1. Synthesis, structures and luminescence properties of amine-bis(N-heterocyclic carbene) copper( i ) and silver( i ) complexes

   https://doi.org/10.1039/C8DT00599K  

   Lu, Taotao; Wang, Jin-Yun; Shi, Lin-Xi; Chen, Zhong-Ning; Chen, Xue-Tai; Xue, Zi-Ling (January 2018, Dalton Transactions)

   A series of Ag( i ) and Cu( i ) complexes [Ag 3 (L 1 ) 2 ][PF 6 ] 3 ( 8 ), [Ag 3 (L 2 ) 2 ][PF 6 ] 3 ( 9 ), [Cu(L 1 )][PF 6 ] ( 10 ) and [Cu(L 2 )][PF 6 ] ( 11 ) have been synthesized by reactions of the tridentate amine-bis(N-heterocyclic carbene) ligand precursors [H 2 L 1 ][PF 6 ] 2 ( 6 ) and [H 2 L 2 ][PF 6 ] 2 ( 7 ) with Ag 2 O and Cu 2 O, respectively. Complexes 10 and 11 can also be obtained by transmetalation of 8 and 9 , respectively, with 3.0 equiv. of CuCl. A heterometallic Cu/Ag–NHC complex [Cu 2 Ag(L 1 ) 2 (CH 3 CN) 2 ][PF 6 ] 3 ( 12 ) is formed by the reaction of 8 with 2.0 equiv. of CuCl. All complexes have been characterized by NMR, electrospray ionization mass spectrometry (ESI-MS), and single-crystal X-ray diffraction studies. The luminescence properties of 10–12 in solution and the solid state have been studied. At room temperature, 10–12 exhibit evident luminescence in solution and the solid state. The emission wavelengths are found to be identical at 483 nm in CH 3 CN, but they are 484, 480 and 592 nm in the solid state for 10–12 , respectively. These results suggest that 12 dissociates into two molecules of 10 and Ag( i ) ions in solution. Complex 12 is the first luminescent heterometallic Cu/Ag–NHC complex. 

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2. Carbene–Calcium Silylamides and Amidoboranes

   https://doi.org/10.1021/acs.organomet.2c00464  

   Obi, Akachukwu D.; Freeman, Lucas A.; Coates, Samuel J.; Alexis, Andrew J.; Frey, Nathan C.; Dickie, Diane A.; Webster, Charles Edwin; Gilliard, Robert J. (November 2022, Organometallics)
3. Carbene reactivity from alkyl and aryl aldehydes

   https://doi.org/10.1126/science.abo6443  

   Zhang, Lumin; DeMuynck, Bethany M.; Paneque, Alyson N.; Rutherford, Joy E.; Nagib, David A. (August 2022, Science)

   Reaction of aldehydes with pivaloyl chloride and then zinc offers versatile and comparatively safe access to carbenes. 

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4. A crystalline monosubstituted carbene

   https://doi.org/10.1038/s41557-018-0153-1  

   Nakano, Ryo; Jazzar, Rodolphe; Bertrand, Guy (December 2018, Nature Chemistry)
5. One-electron bonds in copper–aluminum and copper–gallium complexes

   https://doi.org/10.1039/D2SC01998A  

   Graziano, Brendan J.; Scott, Thais R.; Vollmer, Matthew V.; Dorantes, Michael J.; Young, Victor G.; Bill, Eckhard; Gagliardi, Laura; Lu, Connie C. (June 2022, Chemical Science)

   Odd-electron bonds have unique electronic structures and are often encountered as transiently stable, homonuclear species. In this study, a pair of copper complexes supported by Group 13 metalloligands, M[N(( o -C 6 H 4 )NCH 2 P i Pr 2 ) 3 ] (M = Al or Ga), featuring two-center/one-electron (2c/1e) σ-bonds were synthesized by one-electron reduction of the corresponding Cu( i ) ⇢ M(III) counterparts. The copper bimetallic complexes were investigated by X-ray diffraction, cyclic voltammetry, electron paramagnetic spectroscopy, and density functional theory calculations. The combined experimental and theoretical data corroborate that the unpaired spin is delocalized across Cu, M, and ancillary atoms, and the singly occupied molecular orbital (SOMO) corresponds to a σ-(Cu–M) bond involving the Cu 4p z and M n s/ n p z atomic orbitals. Collectively, the data suggest the covalent nature of these interactions, which represent the first examples of odd-electron σ-bonds for the heavier Group 13 elements Al and Ga. 

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