A Systematic Investigation of Coinage Metal Carbonyl Complexes Stabilized by Fluorinated Alkoxy Aluminates. Issue 37 (29th July 2013)

• Record Type: Journal Article
• Authors: Schaefer, Julia; Kraft, Anne; Reininger, Stefanie; Santiso‐Quinones, Gustavo; Himmel, Daniel; Trapp, Nils; Gellrich, Urs; Breit, Bernhard; Krossing, Ingo
• Is Part Of: Chemistry. Volume 19:Issue 37(2013)
• Page Start: 12468
• Page End: 12485
• Publication Date: 2013-07-29
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201204544
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The reaction of Cu<sup>I</sup>, Ag<sup>I</sup>, and Au<sup>I</sup> salts with carbon monoxide in the presence of weakly coordinating anions led to known and structurally unknown non‐classical coinage metal carbonyl complexes [M(CO)<sub><italic>n</italic></sub>][A] (A=fluorinated alkoxy aluminates). The coinage metal carbonyl complexes [Cu(CO)<sub><italic>n</italic></sub>(CH<sub>2</sub>Cl<sub>2</sub>)<sub><italic>m</italic></sub>]<sup>+</sup>[A]<sup>−</sup> (<italic>n</italic>=1, 3; <italic>m</italic>=4−<italic>n</italic>), [Au<sub>2</sub>(CO)<sub>2</sub>Cl]<sup>+</sup>[A]<sup>−</sup>, [(OC)<sub><italic>n</italic></sub>M(A)] (M=Cu: <italic>n</italic>=2; Ag: <italic>n</italic>=1, 2) as well as [(OC)<sub>3</sub>Cu⋅⋅⋅ClAl(OR<sup>F</sup>)<sub>3</sub>] and [(OC)Au⋅⋅⋅ClAl(OR<sup>F</sup>)<sub>3</sub>] were analyzed with X‐ray diffraction and partially IR and Raman spectroscopy. In addition to these structures, crystallographic and spectroscopic evidence for the existence of the tetracarbonyl complex [Cu(CO)<sub>4</sub>]<sup>+</sup>[Al(OR<sup>F</sup>)<sub>4</sub>]<sup>−</sup> (R<sup>F</sup>=C(CF<sub>3</sub>)<sub>3</sub>) is presented; its formation was analyzed with the help of theoretical investigations and Born–Fajans–Haber cycles. We discuss the limits of structure determinations by routine X‐ray diffraction methods with respect to the CO bond lengths and apply the experimental CO stretching frequencies for the prediction of bond lengths within the carbonyl ligand based on a correlation with calculated data. Moreover, we provide a simple explanation for the reported, partly confusing and scattered CO stretching frequencies of [Cu<sup>I</sup>(CO)<sub><italic>n</italic></sub>] units.</p> </abstract>