2006
DOI: 10.1021/ic0611995
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Chemistry Surrounding Monomeric Copper(I) Methyl, Phenyl, Anilido, Ethoxide, and Phenoxide Complexes Supported by N-Heterocyclic Carbene Ligands:  Reactivity Consistent with Both Early and Late Transition Metal Systems

Abstract: Monomeric copper(I) alkyl complexes that possess the N-heterocyclic carbene (NHC) ligands IPr, SIPr, and IMes [IPr ) 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, SIPr ) 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene, IMes ) 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene] react with amines or alcohols to release alkane and form the corresponding monomeric copper(I) amido, alkoxide, or aryloxide complexes. Thermal decomposition reactions of (NHC)Cu I methyl complexes at temperatures between 100 and 13… Show more

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Cited by 92 publications
(86 citation statements)
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“…[ [87][88][89] Thus, despite substantial MÀX bond dissociation energies (BDEs) for some complexes, [90,91] reactive systems are common, and the enhancement of basicity/nucleophilicity of the ligand X can be exploited for metal-mediated chemistry. [87][88][89][90][91][92][93][94][95][96][97] The basic and nucleophilic character of many late transition metal-X systems has been demonstrated.…”
Section: Transition Metal Complexes With High D-electron Counts That mentioning
confidence: 99%
“…[ [87][88][89] Thus, despite substantial MÀX bond dissociation energies (BDEs) for some complexes, [90,91] reactive systems are common, and the enhancement of basicity/nucleophilicity of the ligand X can be exploited for metal-mediated chemistry. [87][88][89][90][91][92][93][94][95][96][97] The basic and nucleophilic character of many late transition metal-X systems has been demonstrated.…”
Section: Transition Metal Complexes With High D-electron Counts That mentioning
confidence: 99%
“…[155] The phenyl substituent of 1 is also oriented for π-overlap with the amido lone pair (see Figure 4 below Similar to the preparation of Cu-methyl complexes by Sadighi et al, [156] we have employed NHC (NHC = Nheterocyclic carbene) ligands to stabilize monomeric twocoordinate Cu I systems with anionic heteroatomic ligands. [23,25,38] The NHC ligand has been varied between IMes {1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene}, IPr {1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene}, and SIPr {1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene}. (2) studies suggest that the reaction involves the initial coordination of aniline followed by protonation of the methyl ligand.…”
Section: Five-and Six-coordinate (Pcp)ru II Systemsmentioning
confidence: 99%
“…We have structurally characterized three Cu-NHPh complexes: 6 ], which is 1.444(4) Å. [23,30] Consistent with the solid-state structures that suggest a negligible Cu-N amido π-interaction for the Cu I anilido complexes 1-4, the calculated Kohn-Sham (KS) HOMO of these systems has little Cu character, and that which is pres ent is Cu 3d (p amido -d Cu π*) rather than 4p ( Figure 5). [23] However, the KS HOMOs possess a substantial contribution from the phenyl π-system.…”
Section: Five-and Six-coordinate (Pcp)ru II Systemsmentioning
confidence: 99%
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