Dioxygen—Copper Reactivity. Reversible Binding of O2 and CO to a Phenoxo-Bridged Dicopper(I) Complex

Kenneth D. Karlin, Richard W. Cruse, Yilma Gultneh, Amjad Farooq, Jon C. Hayes, Jon Zubieta

Research output: Contribution to journalArticle

183 Scopus citations

Abstract

A chemical system possessing features that mimic certain structural properties and the O2 binding behavior of the active site of the copper-containing dioxygen carrier hemocyanin (He) is presented. A phenolic dinucleating ligand possessing two tridentate py2 units (py2 = bis(2-(2-pyridyl)ethyl)amine) (XYL-OH) forms a phenoxo-bridged dicopper(I) complex, [Cu2(XYL-0-)]PF6(1). At -80 °C in dichloromethane solution, 1 reacts with O2(Cu:O2= 2:1) to give an intensely purple-colored dioxygen adduct, [Cu2(XYL-0-)(O2)]PF6(2), having charge-transfer absorptions in the visible region at 505 (e 6000) and 610 (sh) nm (e 2100 (M'Cm)“1) with additional features at 385 (e 2900), 790 (e 700), and 925 nm (e 600 (M.cm)_1). The binding of O2to 1 is reversible, and the O2 ligand can be removed in vacuo to regenerate 1. This vacuum cycling can be followed spectrophotometrically over several cycles. Carbon monoxide and triphenylphosphine react with 1 to form the bis adducts 3,[cu2(xyl-0-)(c0)2]pf6(3a) and [Cu2(XYL-0-)(PPh3)2]PF6(3b), respectively; the reaction with carbon monoxide is also reversible. The dioxygen adduct 2 reacts with CO and/or PPh3, displacing the bound O2 ligand and producing the adducts 3; this behavior further substantiates that the reaction of 1 with O2 is an equilibrium process. Carbonyl cycling, where 1 reacts with O2to produce 2, O2is displaced by CO to produce 3a, and 3a is decarbonylated to regenerate 1, can also be followed spectrophotometrically over several cycles. In both cycling procedures, a decomposition product is observed and identified as the phenoxo and hydroxo doubly bridged dicopper(II) complex [Cu2(XYL-0)(OH)]2+. Crystallographic studies have been completed for both 1 and 3b. 1 crystallizes in the monoclinic space group P21/n with Z = 8 (2 per asymmetric unit) and a = 13.861 (4) Å, b = 13.482 (8) Å, c = 16.956 (5) Å, and 0 = 98.20 (2)°. Complex 3b crystallizes in the triclinic space group P with Z = 2 and a = 13.410 (3) Å, b = 14.867 (3) Å, c = 18.990 (4) Å, a = 102.35 (2)°, 0 = 91.71 (2)°, and y ~ 98.68 (2)°. While 1 contains two phenoxo-bridged tetracoordinate Cu(I) ions (Cu—Cu = 3.62-3.72 Å) where each copper atom is also coordinated to the py2 tridentate group, in 3b one pyridine donor from each py2 unit remains uncoordinated such that each Cu(I) atom is bound by two nitrogen donors, the P atom from a PPh3 ligand, and the bridging phenoxo oxygen atom (Cu-Cu = 3.992 A).

Original languageEnglish (US)
Pages (from-to)2668-2679
Number of pages12
JournalJournal of the American Chemical Society
Volume109
Issue number9
DOIs
StatePublished - Apr 1 1987
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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