A series of two-coordinate copper tert-butoxide complexes bearing five-, six-, and seven-membered ring N-heterocyclic carbenes, prepared by protonolysis of (NHC)CuMes with t BuOH, have been used as catalytic precursors in the semihydrogenation of alkynes with silanes/ t BuOH and the hydroboration of alkynes with HBPin. Both processes proceed with high regioselectivity and show enhancements with six-and seven-membered ring carbenes.

The photophysical properties of four, two-coordinate, linear diamidocarbene copper(i) complexes, [(DAC)Cu][BF] (1), (DAC)CuOSiPh (2), (DAC)CuCF (3) and (DAC)Cu(2,4,6-MeCH) (4) (DAC = 1,3-bis(2,4,6-trimethylphenyl)-5,5-dimethyl-4,6-diketopyrimidinyl-2-ylidene) have been investigated. Complex 1 shows a high photoluminescence quantum efficiency (Φ) in both the solid state (Φ = 0.85) and in CHCl solution (Φ = 0.65). The emission band of 1, both as a crystalline solid and in solution, is narrow (fwhm = 2300 cm) relative to the emission bands of 2 (fwhm = 2900 cm) and 3 (fwhm = 3700 cm). Complexes 2 and 3 are each brightly luminescent in the solid state (Φ = 0.62 and 0.18, respectively), but markedly less so in CHCl solution (Φ = 0.03 and <0.01, respectively). Complex 4 is not emissive in either the solid state or in solution. Phosphorescence of 1 in CHCl solution shows negligible quenching by oxygen in CHCl solution. This insensitivity to quenching is attributed to the excited state redox potential being insufficient for electron transfer to oxygen.

Dirhodium paddlewheel complexes are indispensable tools in modern organometallic catalysis for the controlled decomposition of diazo-compounds. Tuning the reactivity of the thus-formed transient carbenes remains an active and dynamic field of research. Herein, we present our findings that the distal metal center plays an as yet underappreciated role in modulating this reactivity. Replacement of one rhodium atom in the bimetallic core for bismuth results in the formation of a significantly more electrophilic carbene complex. Bismuth-rhodium catalysts thereby facilitate previously unknown modes of reactivity for α-diazoester compounds, including the cyclopropanation of alkenes as electron deficient as trichloroethylene. While dirhodium paddlewheel complexes remain the catalysts of choice for many carbene-mediated transformations, their bismuth-rhodium analogues exhibit complementary reactivity and show great potential for small molecule and solvent activation chemistry. DFT calculations highlight the importance of metal-metal bonding interactions in controlling carbene electrophilicity. The paucity of these interactions between the 4d orbitals of rhodium and the 6p orbitals of bismuth results in weaker π-back-bonding interactions for bismuth-rhodium carbene complexes compared to dirhodium carbene complexes. This leads to weakening of the rhodium-carbene bond and to a more carbene-centered LUMO, accounting for the observed enhancement in bismuth-rhodium carbene electrophilicity. These findings are supported by a detailed spectroscopic study of the "donor-donor" carbene complexes Rh(esp)C( p-MeOPh) (19) and BiRh(esp)C( p-MeOPh) (20), employing a combination of UV-vis and resonance Raman spectroscopy. The results reveal that carbene chemoselectivity in MRh(L) catalysis can be modulated to a previously unrecognized extent by the distal metalloligand.

The mononuclear N-heterocyclic carbene (NHC) copper alkoxide complexes [(6-NHC)CuOtBu] (6-NHC = 6-MesDAC (1), 6-Mes (2)) have been prepared by addition of the free carbenes to the tetrameric tert-butoxide precursor [Cu(OtBu)]4, or by protonolysis of [(6-NHC)CuMes] (6-NHC = 6-MesDAC (3), 6-Mes (4)) with tBuOH. In contrast to the relatively stable diaminocarbene complex 2, the diamidocarbene derivative 1 proved susceptible to both thermal and hydrolytic ring-opening reactions, the latter affording [(6-MesDAC)Cu(OC(O)CMe2C(O)N(H)Mes)(CNMes)] (6). The intermediacy of [(6-MesDAC)Cu(OH)] in this reaction was supported by the generation of Cu2O as an additional product. Attempts to generate an isolable copper hydride complex of the type [(6-MesDAC)CuH] by reaction of 1 with Et3SiH resulted instead in migratory insertion to generate [(6-MesDAC-H)Cu(P(p-tolyl)3)] (9) upon trapping by P(p-tolyl)3. Migratory insertion was also observed during attempts to prepare [(6-Mes)CuH], with [(6-Mes-H)Cu(6-Mes)] (10) isolated, following a reaction that was significantly slower than in the 6-MesDAC case. The longer lifetime of [(6-Mes)CuH] allowed it to be trapped stoichiometrically by alkyne, and also employed in the catalytic semi-reduction of alkynes and hydrosilylation of ketones.

Cyclopropanation reactions of styrene derivatives with donor–acceptor carbenes formed in situ are significantly more enantioselective when catalyzed by the heterobimetallic bismuth–rhodium complex 5 a endowed with N‐phthalimido tert‐leucine paddlewheel ligands rather than by its homobimetallic dirhodium analogue 1 a. This virtue is likely the result of two synergizing factors: the conical shape of 5 a translates into a narrower calyx‐like chiral binding site about the catalytically active Rh center; the Bi atom, although fully solvent exposed, does not decompose aryl diazoacetates and is hence incapable of promoting a racemic background reaction. Moreover, ligand variation proved that successful catalyst design mandates that the anisotropy of the conical heterobimetallic core be matched by proper directionality of the ligand sphere.

The synthesis of the Cu-borate complexes [(6Mes)Cu(HBR )] featuring the unusual [HBEt ] (5) and [HB(C F ) ] (6) ligands is described. Experimental and computational studies show both compounds feature a direct Cu-H interaction, but that while 5 is two-coordinate, 6 displays an additional, stabilizing Cu-C (C F ) interaction.

Treatment of CuCl with 1 equiv of the in situ prepared N-mesityl-substituted diamidocarbene 6-MesDAC produced a mixture of the dimeric and trimeric copper complexes [(6-MesDAC)CuCl]2 (1) and [(6-MesDAC)2(CuCl)3] (2). Combining CuCl with isolated, free 6-MesDAC in 1:1 and 3:2 ratios gave just 1 and 2, respectively, while increasing the ratio to >5:1 allowed the isolation of small amounts of the tetrameric copper complex [(6-MesDAC)2(CuCl)4] (3). Efforts to bring about metathesis reactions of 1 with MOtBu (M = Li, Na, K) proved successful only for M = Li to afford the spectroscopically characterized ate product [(6-MesDAC)CuCl·LiOtBu·2THF] (5). Attempts to crystallize this species instead gave a 1:1 mixture of 1 and the monomer [(6-MesDAC)CuCl] (6). The X-ray structures of 1–3 and 1 + 6, along with the cation [Cu(6-MesDAC)2]+ (4), have been determined.

The electrophilic character of free diamidocarbenes (DACs) allows them to activate inert bonds in small molecules, such as NH3 and P4 . Herein, we report that metal coordinated DACs also exhibit electrophilic reactivity, undergoing attack by Zn and Cd dialkyl precursors to afford the migratory insertion products [(6-MesDAC-R)MR] (M=Zn, Cd; R=Et, Me; Mes=mesityl). These species were formed via the spectroscopically characterised intermediates [(6-MesDAC)MR2 ], exhibiting barriers to migratory insertion which increase in the order MR2 = ZnEt2 < ZnMe2 < CdMe2 . Compound [(6-MesDAC-Me)CdMe] showed limited stability, undergoing deposition of Cd metal, by an apparent β-H elimination pathway. These results raise doubts about the suitability of diamidocarbenes as ligands in catalytic reactions involving metal species bearing nucleophilic ligands (M-R, M-H).