Highly Electrophilic (Salen)ruthenium(VI) Nitrido Complexes

Wai-Lun Man; Tsz-Man Tang; Tsz-Wing Wong; Tai-Chu Lau; Shie-Ming Peng; Wing-Tak Wong

doi:10.1021/ja037899f

Highly Electrophilic (Salen)ruthenium(VI) Nitrido Complexes

Wai-Lun Man
, Tsz-Man Tang
, Tsz-Wing Wong
, Tai-Chu Lau
, Shie-Ming Peng
, Wing-Tak Wong

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

105 Citations (Scopus)

Abstract

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 [NBuⁿ ₄][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(RuΞN) = 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°. Copyright © 2004 American Chemical Society.

Original language	English
Pages (from-to)	478-479
Journal	Journal of the American Chemical Society
Volume	126
Issue number	2
DOIs	https://doi.org/10.1021/ja037899f
Publication status	Published - 21 Jan 2004

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@article{2cb1f192137948c29030397820c71acf,

title = "Highly Electrophilic (Salen)ruthenium(VI) Nitrido Complexes",

abstract = "A series of cationic ruthenium(VI) nitrido species containing the cyclohexyl-bridged salen ligand (L) and its derivatives, [RuVI(N)(L)]+, have been prepared by treatment of [NBun 4][RuVI(N)Cl4] with H2L in methanol. The structure of [RuVI(N)(L)](ClO4) (1a) has been determined by X-ray crystallography, d(RuΞN) = 1.592 {\AA}. In solvents such as DMF or DMSO, [RuVI(N)(L)]+ undergoes a facile N⋯N coupling reaction at room temperature to produce N2 and [RuIII(L)(S)2]+ (S = solvent). 1a reacts rapidly with secondary amines to produce diamagnetic RuIV-hydrazido(1-) species, [RuIV(N(H)NR2)(L)(HNR2)]+. The reaction with morpholine is first order in RuVI 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-[OsVI(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 {\AA}, and the Ru-N-N angle is 129.4°. Copyright {\textcopyright} 2004 American Chemical Society.",

author = "Wai-Lun Man and Tsz-Man Tang and Tsz-Wing Wong and Tai-Chu Lau and Shie-Ming Peng and Wing-Tak Wong",

year = "2004",

month = jan,

day = "21",

doi = "10.1021/ja037899f",

language = "English",

volume = "126",

pages = "478--479",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Highly Electrophilic (Salen)ruthenium(VI) Nitrido Complexes

AU - Man, Wai-Lun

AU - Tang, Tsz-Man

AU - Wong, Tsz-Wing

AU - Lau, Tai-Chu

AU - Peng, Shie-Ming

AU - Wong, Wing-Tak

PY - 2004/1/21

Y1 - 2004/1/21

N2 - A series of cationic ruthenium(VI) nitrido species containing the cyclohexyl-bridged salen ligand (L) and its derivatives, [RuVI(N)(L)]+, have been prepared by treatment of [NBun 4][RuVI(N)Cl4] with H2L in methanol. The structure of [RuVI(N)(L)](ClO4) (1a) has been determined by X-ray crystallography, d(RuΞN) = 1.592 Å. In solvents such as DMF or DMSO, [RuVI(N)(L)]+ undergoes a facile N⋯N coupling reaction at room temperature to produce N2 and [RuIII(L)(S)2]+ (S = solvent). 1a reacts rapidly with secondary amines to produce diamagnetic RuIV-hydrazido(1-) species, [RuIV(N(H)NR2)(L)(HNR2)]+. The reaction with morpholine is first order in RuVI 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-[OsVI(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°. Copyright © 2004 American Chemical Society.

AB - A series of cationic ruthenium(VI) nitrido species containing the cyclohexyl-bridged salen ligand (L) and its derivatives, [RuVI(N)(L)]+, have been prepared by treatment of [NBun 4][RuVI(N)Cl4] with H2L in methanol. The structure of [RuVI(N)(L)](ClO4) (1a) has been determined by X-ray crystallography, d(RuΞN) = 1.592 Å. In solvents such as DMF or DMSO, [RuVI(N)(L)]+ undergoes a facile N⋯N coupling reaction at room temperature to produce N2 and [RuIII(L)(S)2]+ (S = solvent). 1a reacts rapidly with secondary amines to produce diamagnetic RuIV-hydrazido(1-) species, [RuIV(N(H)NR2)(L)(HNR2)]+. The reaction with morpholine is first order in RuVI 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-[OsVI(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°. Copyright © 2004 American Chemical Society.

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U2 - 10.1021/ja037899f

DO - 10.1021/ja037899f

M3 - RGC 21 - Publication in refereed journal

SN - 0002-7863

VL - 126

SP - 478

EP - 479

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 2

ER -

Highly Electrophilic (Salen)ruthenium(VI) Nitrido Complexes

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