A new class of (mu-eta2:eta2-disulfido)dicopper complexes: synthesis, characterization, and disulfido exchange.
Rare examples of (mu-eta2:eta2-disulfido)dicopper complexes have been prepared from Cu(I) and Cu(II) complexes of beta-diketiminate and anilido-imine supporting ligands. A novel byproduct derived from sulfur functionalization of the methine position of a beta-diketiminate ligand was identified. DFT calculations on [(LCu)2X2] (L = beta-diketiminate, X = O or S) complexes rationalize the absence of a bis(mu-sulfido)dicopper isomer, [Cu2(mu-S)2](2+), in the synthetic reactions, yet predict that a [Cu2(mu-S)2](0) core is a stable product of 2-electron reduction of the [Cu2(mu-eta2:eta2-S2)](2+) unit. Exchange of the disulfido ligand was discovered upon reaction of a (mu-eta2:eta2-disulfido)dicopper complex with a Cu(I) reagent.
Brown
Eric C
EC
Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455, USA.
Aboelella
Nermeen W
NW
Reynolds
Anne M
AM
Aullón
Gabriel
G
Alvarez
Santiago
S
Tolman
William B
WB
D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007097:Imines / Q000737:chemistry; D008024:Ligands; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D013237:Stereoisomerism; D013455:Sulfur / Q000737:chemistry*
D007097:Imines; D008024:Ligands; D009942:Organometallic Compounds; D013455:Sulfur; D003300:Copper; D010100:Oxygen