Synthesis and Structure of Chromium(VI) Nitrido Cyclopentadienyl Complexes

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• 作者：Brennan S. Billow ; Ross D. Bemowski ; Stephen A. DiFranco ; Richard J. Staples ; Aaron L. Odom
• 刊名：Organometallics
• 出版年：2015
• 出版时间：September 28, 2015
• 年：2015
• 卷：34
• 期：18
• 页码：4567-4573
• 全文大小：349K
• ISSN：1520-6041

文摘

A series of rare nitrido cyclopentadienyl complexes have been prepared of chromium(VI). An improved synthesis of NCr(I)(NPrⁱ₂)₂ is provided, which reacts with NaCp to give NCr(畏¹-Cp)(NPrⁱ₂)₂ (1) in 82% isolated yield. The 畏¹-indenyl complex 2 can be prepared using a similar procedure. Replacement of one diisopropylamido ligand was accomplished to prepare NCr(NPrⁱ₂)Cp(O₂CPh) (3), NCr(NPrⁱ₂)Cp(Cl) (4), and [NCr(NPrⁱ₂)Cp(NCMe)]⁺[SbF₆]^{鈭?/sup> (5). In the series, the Cr鈥揅 interactions increase in bond order, 3 < 4 < 5, as the cyclopentadienyl compensates for the decreasing donor ability of the other ligands on chromium. The Ligand Donor Parameters (LDPs) for the 畏1-cyclopentadienyl and 畏1-indenyl ligands were measured as 13.73 and 13.76 kcal/mol, respectively. Compounds 1鈥?b>5 were characterized by single-crystal X-ray diffraction.}