Highly Electrophilic (Salen)ruthenium(VI) Nitrido Complexes

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• 作者：Wai-Lun Man ; Tsz-Man Tang ; Tsz-Wing Wong ; Tai-Chu Lau ; Shie-Ming Peng ; and Wing-Tak Wong
• 刊名：Journal of the American Chemical Society
• 出版年：2004
• 出版时间：January 21, 2004
• 年：2004
• 卷：126
• 期：2
• 页码：478 - 479
• 全文大小：60K
• 年卷期：v.126,no.2(January 21, 2004)
• ISSN：1520-5126

文摘

A series of cationic ruthenium(VI) nitrido species containing the cyclohexyl-bridged salen ligand (L) and its derivatives, [Ru^VI(N)(L)]⁺, have been prepared by treatment of [NBuⁿ₄][Ru^VI(N)Cl₄] with H₂L in methanol. The structure of [Ru^VI(N)(L)](ClO₄) (1a) has been determined by X-ray crystallography, d(RuN) = 1.592 Å. In solvents such as DMF or DMSO, [Ru^VI(N)(L)]⁺ undergoes a facile N···N coupling reaction at room temperature to produce N₂ and [Ru^III(L)(S)₂]⁺ (S = solvent). 1a reacts rapidly with secondary amines to produce diamagnetic Ru^IV-hydrazido(1-) species, [Ru^IV(N(H)NR₂)(L)(HNR₂)]⁺. The reaction with morpholine is first order in Ru^VI and second order in morpholine with k(CH₃CN, 25 C) = 2.08 × 10⁶ M^-2 s^-1. This rate constant is over 4 orders of magnitude larger than that of the corresponding reaction of the electrophilic osmium nitride, trans-[Os^VI(N)(tpy)(Cl)₂]⁺, with morpholine. The structure of [Ru(NHNC₄H₈)(L)(NHC₄H₈)](PF₆)₂ has been determined by X-ray crystallography, the Ru-N(hydrazido) distance is 1.940 Å, and the Ru-N-N angle is 129.4.