Binding and Activation of Small Molecules by Three-Coordinate Cr(I)

• Published in: Journal of the American Chemical Society Vol. 129; no. 26; pp. 8090 - 8091
• Main Authors: Monillas, Wesley H, Yap, Glenn P. A, MacAdams, Leonard A, Theopold, Klaus H
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 04-07-2007
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja0725549

[(i-Pr2Ph)2nacnacCr]2(μ-η2:η2-N2) (2) has been prepared and structurally characterized; it contains a bridging side-on bonded dinitrogen ligand with a N−N distance of 1.249(5) Å. Reactions of this reactive Cr(I) synthon with various small molecules resulted in a series of unusual molecules and transformations; thus CO yielded the binuclear isocarbonyl [(i-Pr2Ph)2nacnacCr]2(CO)(μ-η:η1-CO)2, ethylene gave [(i-Pr2Ph)2nacnacCr]2(μ-η:η2-C2H4), O2 oxidatively added to produce (i-Pr2Ph)2nacnacCr(O)2, and azobenzene afforded the product of NN bond cleavage [(i-Pr2Ph)2nacnacCr]2(μ-NPh)2. 2 can be prepared in good yield and affords a facile entry to low-coordinate Cr(I) coordination chemistry.