Ruthenium carbonyl cluster complexes with oxygen ligands. Reactions between Ru3(CO)12 and 4-methoxyphenol or 2-naphthol. Crystal structure of Ru4(μ3-OC6H4OMe-4)2(μ-Cl)(μ-OC6H4OMe-4)(CO)10, an unusual mixed-valence cluster complex

Tyrone P. Jeynes; Marie P. Cifuentes; Mark G. Humphrey; George A. Koutsantonis; Colin L. Raston

doi:10.1016/0022-328X(94)87075-6

Ruthenium carbonyl cluster complexes with oxygen ligands. Reactions between Ru₃(CO)₁₂ and 4-methoxyphenol or 2-naphthol. Crystal structure of Ru₄(μ₃-OC₆H₄OMe-4)₂(μ-Cl)(μ-OC₆H₄OMe-4)(CO)₁₀, an unusual mixed-valence cluster complex

Tyrone P. Jeynes, Marie P. Cifuentes, Mark G. Humphrey, George A. Koutsantonis, Colin L. Raston

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

7 Citations (Scopus)

Abstract

The reaction between 4-methoxyphenol and Ru₃(CO)₁₂ in cyclohexane has been investigated and found to afford a hexaruthenium 'raft' cluster Ru₆(μ-H)₂(μ₅-η⁷-OC₆H₃OMe-4)(CO)₁₆ (3a), together with tetraruthenium clusters incorporating three (Ru₄(μ₃-OC₆H₄OMe-4)₂(μ-Cl)(μ-OC₆H₄OMe-4)(CO)₁₀ (3b)) or four (Ru₄(μ₃-OC₆H₄OMe-4)₂(μ-OC₆H₄OMe-4)₂(CO)₁₀ (3c)) aryloxo ligands; similarly, reaction of Ru₃(CO)₁₂ with 2-naphthol afforded the analogous Ru₆(μ-H)₂(μ₅-η⁷-OC₁₀H₆)(CO)₁₆ (4a), Ru₄(μ₃-OC₁₀H₇)₂(μ-Cl)(μ-OC₁₀H₇)(CO)₁₀ (4b) and Ru₄(μ₃-OC₁₀H₇)₂(μ-OC₁₀H₇)₂(CO)₁₀ (4c). The source of chloride in 3b and 4b is believed to be carbon tetrachloride contaminant in the cyclohexane. An X-ray diffraction study reveals that 3b contains an Ru₃(CO)₈ unit linked to an Ru(CO)₂ moiety by two asymmetric triply-bridging and one asymmetric doubly-bridging 4-methoxyphenoxo ligands, and an asymmetric doubly-bridging chloro ligand; this interaction is strongly suggestive of a higher oxidation state ruthenium linked to a trinuclear cluster of formally zero oxidation state. The dynamic ¹³C NMR spectra of 4c have been recorded, and are consistent with restricted rotation about the ArO linkage of the μ₂-coordinated naphthoxo ligands at low temperature.

Original language	English
Pages (from-to)	133-143
Number of pages	11
Journal	JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume	476
Issue number	2
DOIs	https://doi.org/10.1016/0022-328X(94)87075-6
Publication status	Published - 23 Aug 1994
Externally published	Yes

Keywords

Carbonyl
Clusters
Crystal structure
Fluxionality
Phenols
Ruthenium

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Jeynes, T. P., Cifuentes, M. P., Humphrey, M. G., Koutsantonis, G. A., & Raston, C. L. (1994). Ruthenium carbonyl cluster complexes with oxygen ligands. Reactions between Ru₃(CO)₁₂ and 4-methoxyphenol or 2-naphthol. Crystal structure of Ru₄(μ₃-OC₆H₄OMe-4)₂(μ-Cl)(μ-OC₆H₄OMe-4)(CO)₁₀, an unusual mixed-valence cluster complex. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 476(2), 133-143. https://doi.org/10.1016/0022-328X(94)87075-6

Jeynes, Tyrone P. ; Cifuentes, Marie P. ; Humphrey, Mark G. et al. / Ruthenium carbonyl cluster complexes with oxygen ligands. Reactions between Ru₃(CO)₁₂ and 4-methoxyphenol or 2-naphthol. Crystal structure of Ru₄(μ₃-OC₆H₄OMe-4)₂(μ-Cl)(μ-OC₆H₄OMe-4)(CO)₁₀, an unusual mixed-valence cluster complex. In: JOURNAL OF ORGANOMETALLIC CHEMISTRY. 1994 ; Vol. 476, No. 2. pp. 133-143.

@article{eff540854f0345549d061e13c8a99e3a,

title = "Ruthenium carbonyl cluster complexes with oxygen ligands. Reactions between Ru3(CO)12 and 4-methoxyphenol or 2-naphthol. Crystal structure of Ru4(μ3-OC6H4OMe-4)2(μ-Cl)(μ-OC6H4OMe-4)(CO)10, an unusual mixed-valence cluster complex",

abstract = "The reaction between 4-methoxyphenol and Ru3(CO)12 in cyclohexane has been investigated and found to afford a hexaruthenium 'raft' cluster Ru6(μ-H)2(μ5-η7-OC6H3OMe-4)(CO)16 (3a), together with tetraruthenium clusters incorporating three (Ru4(μ3-OC6H4OMe-4)2(μ-Cl)(μ-OC6H4OMe-4)(CO)10 (3b)) or four (Ru4(μ3-OC6H4OMe-4)2(μ-OC6H4OMe-4)2(CO)10 (3c)) aryloxo ligands; similarly, reaction of Ru3(CO)12 with 2-naphthol afforded the analogous Ru6(μ-H)2(μ5-η7-OC10H6)(CO)16 (4a), Ru4(μ3-OC10H7)2(μ-Cl)(μ-OC10H7)(CO)10 (4b) and Ru4(μ3-OC10H7)2(μ-OC10H7)2(CO)10 (4c). The source of chloride in 3b and 4b is believed to be carbon tetrachloride contaminant in the cyclohexane. An X-ray diffraction study reveals that 3b contains an Ru3(CO)8 unit linked to an Ru(CO)2 moiety by two asymmetric triply-bridging and one asymmetric doubly-bridging 4-methoxyphenoxo ligands, and an asymmetric doubly-bridging chloro ligand; this interaction is strongly suggestive of a higher oxidation state ruthenium linked to a trinuclear cluster of formally zero oxidation state. The dynamic 13C NMR spectra of 4c have been recorded, and are consistent with restricted rotation about the ArO linkage of the μ2-coordinated naphthoxo ligands at low temperature.",

keywords = "Carbonyl, Clusters, Crystal structure, Fluxionality, Phenols, Ruthenium",

author = "Jeynes, {Tyrone P.} and Cifuentes, {Marie P.} and Humphrey, {Mark G.} and Koutsantonis, {George A.} and Raston, {Colin L.}",

year = "1994",

month = aug,

day = "23",

doi = "10.1016/0022-328X(94)87075-6",

language = "English",

volume = "476",

pages = "133--143",

journal = "JOURNAL OF ORGANOMETALLIC CHEMISTRY",

issn = "0022-328X",

publisher = "Elsevier",

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Jeynes, TP, Cifuentes, MP, Humphrey, MG, Koutsantonis, GA & Raston, CL 1994, 'Ruthenium carbonyl cluster complexes with oxygen ligands. Reactions between Ru₃(CO)₁₂ and 4-methoxyphenol or 2-naphthol. Crystal structure of Ru₄(μ₃-OC₆H₄OMe-4)₂(μ-Cl)(μ-OC₆H₄OMe-4)(CO)₁₀, an unusual mixed-valence cluster complex', JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 476, no. 2, pp. 133-143. https://doi.org/10.1016/0022-328X(94)87075-6

Ruthenium carbonyl cluster complexes with oxygen ligands. Reactions between Ru₃(CO)₁₂ and 4-methoxyphenol or 2-naphthol. Crystal structure of Ru₄(μ₃-OC₆H₄OMe-4)₂(μ-Cl)(μ-OC₆H₄OMe-4)(CO)₁₀, an unusual mixed-valence cluster complex. / Jeynes, Tyrone P.; Cifuentes, Marie P.; Humphrey, Mark G. et al.
In: JOURNAL OF ORGANOMETALLIC CHEMISTRY, Vol. 476, No. 2, 23.08.1994, p. 133-143.

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

TY - JOUR

T1 - Ruthenium carbonyl cluster complexes with oxygen ligands. Reactions between Ru3(CO)12 and 4-methoxyphenol or 2-naphthol. Crystal structure of Ru4(μ3-OC6H4OMe-4)2(μ-Cl)(μ-OC6H4OMe-4)(CO)10, an unusual mixed-valence cluster complex

AU - Jeynes, Tyrone P.

AU - Cifuentes, Marie P.

AU - Humphrey, Mark G.

AU - Koutsantonis, George A.

AU - Raston, Colin L.

PY - 1994/8/23

Y1 - 1994/8/23

N2 - The reaction between 4-methoxyphenol and Ru3(CO)12 in cyclohexane has been investigated and found to afford a hexaruthenium 'raft' cluster Ru6(μ-H)2(μ5-η7-OC6H3OMe-4)(CO)16 (3a), together with tetraruthenium clusters incorporating three (Ru4(μ3-OC6H4OMe-4)2(μ-Cl)(μ-OC6H4OMe-4)(CO)10 (3b)) or four (Ru4(μ3-OC6H4OMe-4)2(μ-OC6H4OMe-4)2(CO)10 (3c)) aryloxo ligands; similarly, reaction of Ru3(CO)12 with 2-naphthol afforded the analogous Ru6(μ-H)2(μ5-η7-OC10H6)(CO)16 (4a), Ru4(μ3-OC10H7)2(μ-Cl)(μ-OC10H7)(CO)10 (4b) and Ru4(μ3-OC10H7)2(μ-OC10H7)2(CO)10 (4c). The source of chloride in 3b and 4b is believed to be carbon tetrachloride contaminant in the cyclohexane. An X-ray diffraction study reveals that 3b contains an Ru3(CO)8 unit linked to an Ru(CO)2 moiety by two asymmetric triply-bridging and one asymmetric doubly-bridging 4-methoxyphenoxo ligands, and an asymmetric doubly-bridging chloro ligand; this interaction is strongly suggestive of a higher oxidation state ruthenium linked to a trinuclear cluster of formally zero oxidation state. The dynamic 13C NMR spectra of 4c have been recorded, and are consistent with restricted rotation about the ArO linkage of the μ2-coordinated naphthoxo ligands at low temperature.

AB - The reaction between 4-methoxyphenol and Ru3(CO)12 in cyclohexane has been investigated and found to afford a hexaruthenium 'raft' cluster Ru6(μ-H)2(μ5-η7-OC6H3OMe-4)(CO)16 (3a), together with tetraruthenium clusters incorporating three (Ru4(μ3-OC6H4OMe-4)2(μ-Cl)(μ-OC6H4OMe-4)(CO)10 (3b)) or four (Ru4(μ3-OC6H4OMe-4)2(μ-OC6H4OMe-4)2(CO)10 (3c)) aryloxo ligands; similarly, reaction of Ru3(CO)12 with 2-naphthol afforded the analogous Ru6(μ-H)2(μ5-η7-OC10H6)(CO)16 (4a), Ru4(μ3-OC10H7)2(μ-Cl)(μ-OC10H7)(CO)10 (4b) and Ru4(μ3-OC10H7)2(μ-OC10H7)2(CO)10 (4c). The source of chloride in 3b and 4b is believed to be carbon tetrachloride contaminant in the cyclohexane. An X-ray diffraction study reveals that 3b contains an Ru3(CO)8 unit linked to an Ru(CO)2 moiety by two asymmetric triply-bridging and one asymmetric doubly-bridging 4-methoxyphenoxo ligands, and an asymmetric doubly-bridging chloro ligand; this interaction is strongly suggestive of a higher oxidation state ruthenium linked to a trinuclear cluster of formally zero oxidation state. The dynamic 13C NMR spectra of 4c have been recorded, and are consistent with restricted rotation about the ArO linkage of the μ2-coordinated naphthoxo ligands at low temperature.

KW - Carbonyl

KW - Clusters

KW - Crystal structure

KW - Fluxionality

KW - Phenols

KW - Ruthenium

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U2 - 10.1016/0022-328X(94)87075-6

DO - 10.1016/0022-328X(94)87075-6

M3 - Article

AN - SCOPUS:0011411980

SN - 0022-328X

VL - 476

SP - 133

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JO - JOURNAL OF ORGANOMETALLIC CHEMISTRY

JF - JOURNAL OF ORGANOMETALLIC CHEMISTRY

IS - 2

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Jeynes TP, Cifuentes MP, Humphrey MG, Koutsantonis GA, Raston CL. Ruthenium carbonyl cluster complexes with oxygen ligands. Reactions between Ru₃(CO)₁₂ and 4-methoxyphenol or 2-naphthol. Crystal structure of Ru₄(μ₃-OC₆H₄OMe-4)₂(μ-Cl)(μ-OC₆H₄OMe-4)(CO)₁₀, an unusual mixed-valence cluster complex. JOURNAL OF ORGANOMETALLIC CHEMISTRY. 1994 Aug 23;476(2):133-143. doi: 10.1016/0022-328X(94)87075-6