Dinuclear ruthenium nitrido complexes supported by an oxygen tripodal ligand

Xiao Yi Yi; Ho Yuen Ng; Wai Man Cheung; Herman H.Y. Sung; Ian D. Williams; Wa Hung Leung

doi:10.1021/ic300638r

Dinuclear ruthenium nitrido complexes supported by an oxygen tripodal ligand

Xiao Yi Yi, Ho Yuen Ng, Wai Man Cheung, Herman H.Y. Sung, Ian D. Williams, Wa Hung Leung^*

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Journal Article › peer-review

20 Citations (Scopus)

Abstract

Dinuclear ruthenium nitrido complexes supported by the Kläuis tripodal ligand [CpCo{P(O)(OEt) ₂} ₃] ^- (L _OEt ^-) have been synthesized starting from the ruthenium(VI) nitrido precursor [L _OEtRu ^VI(N)Cl ₂] (1). Heating a solution of 1 in CCl ₄ at reflux, followed by recrystallization from hexane under nitrogen, afforded the mixed-valence ruthenium(V)-ruthenium(IV) μ-nitrido complex [L _OEtCl ₂Ru ^V(μ-N)Ru ^IVCl ₂L _OEt] (2). The cyclic voltammogram of 2 exhibited reversible couples at 0.19 and 1.13 V versus Cp ₂Fe ^+/0, which are assigned as the Ru ^V-Ru ^IV/Ru ^IV-Ru ^IV and Ru ^V-Ru ^V/Ru ^V-Ru ^IV couples, respectively. Recrystallization of 2 from Et ₂O/heptane in air yielded the diamagnetic Ru ^IV-Ru ^IV complex [H ₁₃O ₆][{L _OEtRu ^IVCl ₂} ₂(μ-N)] ([H ₁₃O ₆][2]), which underwent cation exchange with n-Bu ₄NOH to give [n-Bu ₄N][2]. X-ray diffraction revealed that the complex anions in [H ₁₃O ₆][2] and [n-Bu ₄N][2] contain linear, symmetric Ru-N-Ru bridges. Treatment of 1 with [(η ⁶-p-cymene)Ru ^IICl ₂] ₂ in benzene afforded the tetranuclear ruthenium(IV) complex [L _OEtCl ₂Ru ^IV(μ-N)Ru ^IV(H ₂O)Cl ₂] ₂ (3) containing symmetric Ru ^IV-N-Ru ^IV bridges. The reaction of 1 with [Ru ^II(H)(Cl)(CO)(PCy ₃) ₂] (Cy = cyclohexyl) gave the ruthenium(VI)-ruthenium(II) nitrido complex [L _OEtCl ₂Ru ^VI(μ-N)Ru ^II(H)Cl(CO)(PCy ₃) ₂] (4). The observed short Ru ^II-N bond distance [1.915(5) Å] and high C-O stretching frequency (1985 cm ^-1) in 4 are suggestive of π interaction between Ru ^II and the nitride.

Original language	English
Pages (from-to)	10529-10535
Number of pages	7
Journal	Inorganic Chemistry
Volume	51
Issue number	20
DOIs	https://doi.org/10.1021/ic300638r
Publication status	Published - 15 Oct 2012

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@article{331030edbc7a42adaad2d260acb7fdcf,

title = "Dinuclear ruthenium nitrido complexes supported by an oxygen tripodal ligand",

abstract = "Dinuclear ruthenium nitrido complexes supported by the Kl{\"a}uis tripodal ligand [CpCo\{P(O)(OEt) 2\} 3] - (L OEt -) have been synthesized starting from the ruthenium(VI) nitrido precursor [L OEtRu VI(N)Cl 2] (1). Heating a solution of 1 in CCl 4 at reflux, followed by recrystallization from hexane under nitrogen, afforded the mixed-valence ruthenium(V)-ruthenium(IV) μ-nitrido complex [L OEtCl 2Ru V(μ-N)Ru IVCl 2L OEt] (2). The cyclic voltammogram of 2 exhibited reversible couples at 0.19 and 1.13 V versus Cp 2Fe +/0, which are assigned as the Ru V-Ru IV/Ru IV-Ru IV and Ru V-Ru V/Ru V-Ru IV couples, respectively. Recrystallization of 2 from Et 2O/heptane in air yielded the diamagnetic Ru IV-Ru IV complex [H 13O 6][\{L OEtRu IVCl 2\} 2(μ-N)] ([H 13O 6][2]), which underwent cation exchange with n-Bu 4NOH to give [n-Bu 4N][2]. X-ray diffraction revealed that the complex anions in [H 13O 6][2] and [n-Bu 4N][2] contain linear, symmetric Ru-N-Ru bridges. Treatment of 1 with [(η 6-p-cymene)Ru IICl 2] 2 in benzene afforded the tetranuclear ruthenium(IV) complex [L OEtCl 2Ru IV(μ-N)Ru IV(H 2O)Cl 2] 2 (3) containing symmetric Ru IV-N-Ru IV bridges. The reaction of 1 with [Ru II(H)(Cl)(CO)(PCy 3) 2] (Cy = cyclohexyl) gave the ruthenium(VI)-ruthenium(II) nitrido complex [L OEtCl 2Ru VI(μ-N)Ru II(H)Cl(CO)(PCy 3) 2] (4). The observed short Ru II-N bond distance [1.915(5) {\AA}] and high C-O stretching frequency (1985 cm -1) in 4 are suggestive of π interaction between Ru II and the nitride.",

author = "Yi, \{Xiao Yi\} and Ng, \{Ho Yuen\} and Cheung, \{Wai Man\} and Sung, \{Herman H.Y.\} and Williams, \{Ian D.\} and Leung, \{Wa Hung\}",

year = "2012",

month = oct,

day = "15",

doi = "10.1021/ic300638r",

language = "English",

volume = "51",

pages = "10529--10535",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "20",

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TY - JOUR

T1 - Dinuclear ruthenium nitrido complexes supported by an oxygen tripodal ligand

AU - Yi, Xiao Yi

AU - Ng, Ho Yuen

AU - Cheung, Wai Man

AU - Sung, Herman H.Y.

AU - Williams, Ian D.

AU - Leung, Wa Hung

PY - 2012/10/15

Y1 - 2012/10/15

N2 - Dinuclear ruthenium nitrido complexes supported by the Kläuis tripodal ligand [CpCo{P(O)(OEt) 2} 3] - (L OEt -) have been synthesized starting from the ruthenium(VI) nitrido precursor [L OEtRu VI(N)Cl 2] (1). Heating a solution of 1 in CCl 4 at reflux, followed by recrystallization from hexane under nitrogen, afforded the mixed-valence ruthenium(V)-ruthenium(IV) μ-nitrido complex [L OEtCl 2Ru V(μ-N)Ru IVCl 2L OEt] (2). The cyclic voltammogram of 2 exhibited reversible couples at 0.19 and 1.13 V versus Cp 2Fe +/0, which are assigned as the Ru V-Ru IV/Ru IV-Ru IV and Ru V-Ru V/Ru V-Ru IV couples, respectively. Recrystallization of 2 from Et 2O/heptane in air yielded the diamagnetic Ru IV-Ru IV complex [H 13O 6][{L OEtRu IVCl 2} 2(μ-N)] ([H 13O 6][2]), which underwent cation exchange with n-Bu 4NOH to give [n-Bu 4N][2]. X-ray diffraction revealed that the complex anions in [H 13O 6][2] and [n-Bu 4N][2] contain linear, symmetric Ru-N-Ru bridges. Treatment of 1 with [(η 6-p-cymene)Ru IICl 2] 2 in benzene afforded the tetranuclear ruthenium(IV) complex [L OEtCl 2Ru IV(μ-N)Ru IV(H 2O)Cl 2] 2 (3) containing symmetric Ru IV-N-Ru IV bridges. The reaction of 1 with [Ru II(H)(Cl)(CO)(PCy 3) 2] (Cy = cyclohexyl) gave the ruthenium(VI)-ruthenium(II) nitrido complex [L OEtCl 2Ru VI(μ-N)Ru II(H)Cl(CO)(PCy 3) 2] (4). The observed short Ru II-N bond distance [1.915(5) Å] and high C-O stretching frequency (1985 cm -1) in 4 are suggestive of π interaction between Ru II and the nitride.

AB - Dinuclear ruthenium nitrido complexes supported by the Kläuis tripodal ligand [CpCo{P(O)(OEt) 2} 3] - (L OEt -) have been synthesized starting from the ruthenium(VI) nitrido precursor [L OEtRu VI(N)Cl 2] (1). Heating a solution of 1 in CCl 4 at reflux, followed by recrystallization from hexane under nitrogen, afforded the mixed-valence ruthenium(V)-ruthenium(IV) μ-nitrido complex [L OEtCl 2Ru V(μ-N)Ru IVCl 2L OEt] (2). The cyclic voltammogram of 2 exhibited reversible couples at 0.19 and 1.13 V versus Cp 2Fe +/0, which are assigned as the Ru V-Ru IV/Ru IV-Ru IV and Ru V-Ru V/Ru V-Ru IV couples, respectively. Recrystallization of 2 from Et 2O/heptane in air yielded the diamagnetic Ru IV-Ru IV complex [H 13O 6][{L OEtRu IVCl 2} 2(μ-N)] ([H 13O 6][2]), which underwent cation exchange with n-Bu 4NOH to give [n-Bu 4N][2]. X-ray diffraction revealed that the complex anions in [H 13O 6][2] and [n-Bu 4N][2] contain linear, symmetric Ru-N-Ru bridges. Treatment of 1 with [(η 6-p-cymene)Ru IICl 2] 2 in benzene afforded the tetranuclear ruthenium(IV) complex [L OEtCl 2Ru IV(μ-N)Ru IV(H 2O)Cl 2] 2 (3) containing symmetric Ru IV-N-Ru IV bridges. The reaction of 1 with [Ru II(H)(Cl)(CO)(PCy 3) 2] (Cy = cyclohexyl) gave the ruthenium(VI)-ruthenium(II) nitrido complex [L OEtCl 2Ru VI(μ-N)Ru II(H)Cl(CO)(PCy 3) 2] (4). The observed short Ru II-N bond distance [1.915(5) Å] and high C-O stretching frequency (1985 cm -1) in 4 are suggestive of π interaction between Ru II and the nitride.

UR - https://www.webofscience.com/wos/woscc/full-record/WOS:000309739100010

UR - https://openalex.org/W2036823723

UR - https://www.scopus.com/pages/publications/84867519671

U2 - 10.1021/ic300638r

DO - 10.1021/ic300638r

M3 - Journal Article

SN - 0020-1669

VL - 51

SP - 10529

EP - 10535

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 20

ER -

Dinuclear ruthenium nitrido complexes supported by an oxygen tripodal ligand

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