Copper(I) oxalate complexes: Synthesis, structures and surprises. (24th November 2016)

• Record Type: Journal Article
• Authors: Royappa, A. Timothy; Royappa, Andrew D.; Moral, Raphael F.; Rheingold, Arnold L.; Papoular, Robert J.; Blum, Deke M.; Duong, Tien Q.; Stepherson, Jacob R.; Vu, Oliver D.; Chen, Banghao; Suchomel, Matthew R.; Golen, James A.; André, Gilles; Kourkoumelis, Nikolaos; Mercer, Andrew D.; Pekarek, Allegra M.; Kelly, Dylan C.
• Is Part Of: Polyhedron. Volume 119(2016)
• Page Start: 563
• Page End: 574
• Publication Date: 2016-11-24
• Subjects: Copper(I) oxide -- Oxalate complexes -- Coordination compounds -- Chemical vapor deposition -- Oxalic acid; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2016.09.043
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: A series of copper(I) oxalate complexes was synthesized by the simple reaction of Cu2 O with oxalic acid in ethanol, and structurally characterized by X-ray diffraction, shedding light on their general structure and the mechanism of their disproportionation. Abstract: A series of dinuclear copper(I) oxalate complexes was synthesized by the direct acid-base reaction of Cu2 O with oxalic acid in ethanol with a ligand, or in neat ligand. The complexes incorporated a variety of ligands L (L = triphenylphosphine, 1, 2-bis(diphenylphosphino)ethane, triphenylphosphite, diisopropyl sulfide, cyclooctadiene and cyclohexylisocyanide) and had the general formula L n Cu(μ2 -C2 O4 )CuL n ( n = 1 or 2). The Cu I /Cu II mixed-valence trinuclear compound (iPr2 S)2 Cu I (C2 O4 )Cu II (C2 O4 )Cu I (iPr2 S)2 was formed concomitantly with the target dinuclear Cu2 C2 O4 (iPr2 S)4 complex, shedding light on the mechanism of disproportionation of this family of complexes. With norbornadiene (nbd) as a ligand, however, a coordination polymer Cu2 C2 O4 (nbd) was formed. Also, the same reaction with L = 2, 9-dimethyl-1, 10-phenanthroline or pyridine resulted in the known tetrahedral complex ions [CuL m ] + ( m = 2 or 4). Lastly, the ligand di-2-(1-di-(2-picolyl)amino)propyl disulfide produced not the expected Cu(I) oxalate complex, but a Cu(II) picolylamine oxalate coordination polymer. All products were structurally characterized by single-crystal X-ray diffraction if soluble, and by powder X-ray diffraction methods if not.