Three-Coordinate Copper(II) Aryls: Key Intermediates in C-O Bond Formation.

Copper(II) aryl species are proposed key intermediates in Cu-catalyzed cross-coupling reactions. Novel three-coordinate copper(II) aryls [CuII]-C6F5 supported by ancillary ß-diketiminate ligands form in reactions between copper(II) alkoxides [CuII]-OtBu and B(C6F5)3. Crystallographic, spectroscopic, and DFT studies reveal geometric and electronic structures of these Cu(II) organometallic complexes. Reaction of [CuII]-C6F5 with the free radical NO(g) results in C-N bond formation to give [Cu](η2-ONC6F5). Remarkably, addition of the phenolate anion PhO- to [CuII]-C6F5 directly affords diaryl ether PhO-C6F5 with concomitant generation of the copper(I) species [CuI](solvent) and {[CuI]-C6F5}-. Experimental and computational analysis supports redox disproportionation between [CuII]-C6F5 and {[CuII](C6F5)(OPh)}- to give {[CuI]-C6F5}- and [CuIII](C6F5)(OPh) unstable toward reductive elimination to [CuI](solvent) and PhO-C6F5.

A copper(II) thiolate from reductive cleavage of an S-nitrosothiol.

S-Nitrosothiols RSNO represent circulating reservoirs of nitric oxide activity in the plasma and play intricate roles in protein function control in health and disease. While nitric oxide has been shown to reductively nitrosylate copper(II) centers to form copper(I) complexes and ENO species (E = R(2)N, RO), well-characterized examples of the reverse reaction are rare. Employing the copper(I) ß-diketiminate [Me(2)NN]Cu, we illustrate a clear example in which an RS-NO bond is cleaved to release NO(gas) with formation of a discrete copper(II) thiolate. The addition of Ph(3)CSNO to [Me(2)NN]Cu generates the three-coordinate copper(II) thiolate [Me(2)NN]CuSCPh(3), which is unstable toward free NO.

Nitric oxide oxidatively nitrosylates Ni(I) and Cu(I) C-organonitroso adducts.

Monovalent nickel and copper beta-diketiminato complexes react with ArN=O (Ar = 3,5-Me(2)C(6)H(3), Ph) to give C-nitroso adducts that exhibit three different modes of bonding with varying degrees of N-O bond activation. The addition of ArNO to 2 equiv of [Me(2)NN]Ni(2,4-lutidine) {[Me(2)NN](-) = 2,4-bis(2,6-dimethylphenylimido)pentyl} gives {[Me(2)NN]Ni}(2)(mu-eta(2):eta(2)-ONAr) (1a and 1b), which exhibit symmetrical bonding of the ArN=O moiety between two [Me(2)NN]Ni fragments, with a N-O bond distance of 1.440(4) A in 1a that is significantly longer than those in free C-organonitroso compounds (1.13-1.29 A). [Me(2)NN]Cu(NCMe) reacts with 0.5 equiv of ArNO in ether to give the dinuclear adducts {[Me(2)NN]Cu}(2)(mu-eta(2):eta(1)-ONAr) (2a and 2b), which exhibit eta(2) and eta(1) bonding of the ArN=O moiety with separate [Me(2)NN]Cu fragments possessing N-O distances of 1.375(6) A (2a) and 1.368(2) A (2b). In arene solvents, one beta-diketiminatocopper(I) fragment dissociates from 2 to give [Me(2)NN]Cu(eta(2)-ONAr) (3a and 3b), which may be isolated by the addition of 1 equiv of ArNO to [Me(2)NN]Cu(NCMe). The X-ray structures of 3a and 3b are similar to those of related Cu(I) alkene adducts, with N-O distances in the narrow range 1.333(4)-1.338(5) A. IR spectra of the nitrosobenzene adducts 1b, 2b, and 3b exhibit nu(NO) stretching frequencies at 915, 1040, and 1113 cm(-1), respectively, following the decreasing degree of N=O activation observed in the X-ray structures of species 1, 2, and 3. Both 1a and 3a react with anaerobic NO(g) to give the corresponding N-aryl-N-nitrosohydroxylaminato complexes [Me(2)NN]M(kappa(2)-O(2)N(2)Ar) [M = Ni (4), Cu (5)]. In the reaction of dinuclear 1a with NO, one [Me(2)NN]Ni fragment is trapped as the nickel nitrosyl [Me(2)NN]Ni(NO). Reaction of the monovalent complex [Me(2)NN]Cu(eta(2)-ONAr) with NO(g) to give divalent [Me(2)NN]Cu(kappa(2)-O(2)N(2)Ar) represents an example of oxidative nitrosylation.

Re-evaluating the Cu K pre-edge XAS transition in complexes with covalent metal-ligand interactions.

Three [Me2NN]Cu(η2-L2) complexes (Me2NN = HC[C(Me)NAr]2; L2 = PhNO (2), (3), PhCH[double bond, length as m-dash]CH2 (4); Ar = 2,6-Me2-C6H3; ArF = 3,5-(CF3)2-C6H3) have been studied by Cu K-edge X-ray absorption spectroscopy, as well as single- and multi-reference computational methods (DFT, TD-DFT, CASSCF, MRCI, and OVB). The study was extended to a range of both known and theoretical compounds bearing 2p-element donors as a means of deriving a consistent view of how the pre-edge transition energy responds in systems with significant ground state covalency. The ground state electronic structures of many of the compounds under investigation were found to be strongly influenced by correlation effects, resulting in ground state descriptions with majority contributions from a configuration comprised of a Cu(ii) metal center anti-ferromagentically coupled to radical anion O2, PhNO, and ligands. In contrast, the styrene complex 4, which displays a Cu K pre-edge transition despite its formal d10 electron configuration, exhibits what can best be described as a Cu(i):(styrene)0 ground state with strong π-backbonding. The Cu K pre-edge features for these complexes increase in energy from 1 to 4, a trend that was tracked to the percent Cu(ii)-character in the ground state. The unexpected shift to higher pre-edge transition energies with decreasing charge on copper (Q Cu) contributed to an assignment of the pre-edge features for these species as arising from metal-to-ligand charge transfer instead of the traditional Cu1s → Cu3d designation.