A Systematic Investigation of Coinage Metal Carbonyl Complexes Stabilized by Fluorinated Alkoxy Aluminates |
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Authors: | Dipl.‐Chem. Julia Schaefer Dipl.‐Chem. Anne Kraft Stefanie Reininger Dr. Gustavo Santiso‐Quinones Dr. Daniel Himmel Dr. Nils Trapp Dipl.‐Chem. Urs Gellrich Prof. Dr. Bernhard Breit Prof. Dr. Ingo Krossing |
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Affiliation: | 1. Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum (FMF) and Freiburg Institute for Advanced Studies (FRIAS), Section Soft Matter Science, Universit?t Freiburg, Albertstrasse 19, 79104 Freiburg (Germany);2. ETH, Inorg. Chem. Lab, 8093 Zürich (Switzerland);3. Institut für Organische Chemie und Biochemie, Albertstrasse 21, 79104 Freiburg (Germany) |
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Abstract: | The reaction of CuI, AgI, and AuI 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)n][A] (A=fluorinated alkoxy aluminates). The coinage metal carbonyl complexes [Cu(CO)n(CH2Cl2)m]+[A]? (n=1, 3; m=4?n), [Au2(CO)2Cl]+[A]?, [(OC)nM(A)] (M=Cu: n=2; Ag: n=1, 2) as well as [(OC)3Cu???ClAl(ORF)3] and [(OC)Au???ClAl(ORF)3] 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)4]+[Al(ORF)4]? (RF=C(CF3)3) 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 [CuI(CO)n] units. |
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Keywords: | carbon monoxide carbonyl ligands coinage metals density functional calculations weakly coordinating anions |
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