Paramagnetic Chromium(II) Complexes and Chromium(IV) Nitrides with Bulky Alkylcyclopentadienyl Ligands

• Published in: European journal of inorganic chemistry Vol. 2018; no. 40; pp. 4472 - 4480
• Main Authors: Gidt, Wjatscheslaw, Smytschkow, Igor, Sun, Yu, Langer, Jens, Böttcher, Tobias, Kratzert, Daniel, Klingele, Julia, Oelkers, Benjamin, Sitzmann, Helmut
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 01-11-2018
• Subjects: Acetates; Chromium; Chromium nitride; Cluster compounds; Cubane; Cyclopentadienyl ligands; Dimers; Halides; Heptanes; High‐spin complexes; Inorganic chemistry; Lithium; N ligands; Organic chemistry; Sodium azides; Tetrahydrofuran
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201800901

Easily available chromium(II) acetate was used for an entry into chromium chemistry: sodium tetraisopropylcyclopentadienide (Na4Cp), sodium 1,2,4‐tri(tert‐butyl)cyclopentadienide (NaCp′′′), or lithium pentaisopropylcyclopentadienide (Li5Cp) convert the acetate to the acetate‐bridged dimers [4CpCr(µ‐OOCCH3)]2 (1a), [Cp′′′Cr(µ‐OOCCH3)]2 (1b), or [5CpCr(µ‐OOCCH3)]2 (1c) in yields well above 70 %. These acetates could be converted into the halide‐bridged dimers [4CpCr(µ‐Cl)]2 (2a), [4CpCr(µ‐Br)]2 (3a), [Cp′′′Cr(µ‐Br)]2 (3b), or [5CpCr(µ‐Br)]2 (3c), [4CpCr(µ‐I)]2 (4a), or [Cp′′′Cr(µ‐I)]2 (4b) with the corresponding trimethylsilyl halides in nearly quantitative yield. With bis(trimethylsilyl)sulfate the acetate 1a gave crude bis(tetraisopropylcyclopentadienylchromium)sulfate (5a). From the bromide 3b and sodium bis(trimethylsilyl)amide the mononuclear chromium(II) silylamide [Cp′′′CrN(SiMe3)2(THF)] (7b) was obtained as a tetrahydrofuran adduct. Upon reaction with sodium azide, the iodide 4a afforded the tetranuclear chromium(IV) nitride cubane [(4CpCr)3(µ3‐N)4CrOH] (8a) after extraction with heptane containing traces of water. The analogous chromium nitride derivative [(Cp′′′Cr)3(µ3‐N)4CrBr] (9b) was obtained from the bromide 3b and sodium azide.
A facile entry into reactive alkylcyclopentadienylchromium(II) starting compounds afforded the chromium(IV) nitride cubane shown above from chromium(II) acetate in three steps using sodium tri(tert‐butyl)cyclopentadienide, trimethylsilylbromide, and sodium azide via the chromium(II) bromide intermediate [Cp′′′Cr(µ‐Br)]2. Three tert‐butyl groups per ring ligand have been omitted for clarity.