Use of the cationic fragments [Ru(η5-C5H 5)(MeCN)3]+ and [M(η6-C 6H5R)(MeCN)3]+ (M=Os, Ru; R=H, Me) as ionic coupling reagents with the anions

Muna R.A. Al-Mandhary; Radchada Buntem; Christopher Cathey; Jack Lewis; M. Carmen Ramirez De Arellano; Gregory P. Shields; Cheryl L. Doherty; Paul R. Raithby

doi:10.1016/S0020-1693(02)01516-5

Use of the cationic fragments [Ru(η⁵-C₅H ₅)(MeCN)₃]⁺ and [M(η⁶-C ₆H₅R)(MeCN)₃]⁺ (M=Os, Ru; R=H, Me) as ionic coupling reagents with the anions

Muna R.A. Al-Mandhary, Radchada Buntem, Christopher Cathey, Jack Lewis, M. Carmen Ramirez De Arellano, Gregory P. Shields, Cheryl L. Doherty, Paul R. Raithby^*

^*Corresponding author for this work

Chemistry

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

14 Citations (Scopus)

Abstract

The cluster [H₂Os₄(CO)₁₃] may be reduced with K/Ph₂CO to generate an anion which reacts with [M(η ⁶-C₆H₅R)(MeCN)₃]²⁺ (M=Os, Ru; R=H, Me) affording the capped clusters [H₂Os₄M(CO) ₁₂(η⁶-C₆H₅R)] (M=Os, R=H (1); M=Ru, R=H (2); M=Os, R=Me (3)) with the arene ligand on one of the axial site of a trigonal bipyramid. The Os clusters 1 and 3 transform into the more stable equatorial isomers, 4 and 5, respectively, in 24 h. The structure of 5 has been confirmed by a single crystal X-ray diffraction study, and all the complexes have been characterised spectroscopically. The axial isomers may be carbonylated or hydrogenated to generate the edge-bridged tetrahedral clusters [H₂Os₄M(CO)₁₃(η⁶-C ₆H₅R)] (M=Os, R=H (6); M=Ru, R=H (7); M=Os, R=Me (8)) and the known clusters [H₄Os₄M(CO)₁₂(η ⁶-C₆H₆)] (M=Os (9); Ru (10)). The structure of 7 has been confirmed by an X-ray diffraction analysis. The axial isomer 1 reacts with PPh₂Me to yield the addition product [H ₂Os₅(CO)₁₂(η⁶-C ₆H₆)PPh₂Me] (11), whereas the mixed osmium-ruthenium analogue undergoes a transformation to the 'spiked' tetrahedral [H₃Os₄Ru(CO)₁₂(μ ₃-σ,σ,η⁶-C₆H ₅)PPh₂Me] (12). Deprotonation of the axial isomers 1 and 2 and subsequent reaction with [AuPPh₃]⁺ yields [HOs ₄M(CO)₁₂(C₆H₆)(AuPPh₃)] (M=Os (13); Ru (14)). As well as spectroscopic characterisation cluster, the structures of 11, 12 and 13 have been established by X-ray diffraction experiments. In a related series of reactions the cluster monoanion [Os ₄(CO)₁₃X]^- (X=Cl (15), Br (16), I (17)) may be capped using the monocation [Ru(η⁵-C₅H ₅)(MeCN)₃]⁺ affording [HOs₄Ru(CO) ₁₃(η⁵-C₅H₅)] (18), which is readily deprotonated and further capped with [AuPPh₃]⁺ to afford the neutral cluster [Os₄(CO)₁₃Ru(η ⁵-C₅H₅)AuPPh₃] (20). The structures of 15, 18 and 20 have been established crystallographically. The cluster anion [Os₄(CO)₁₃X]^- may be reduced with K/Ph ₂CO and the resulting anionic complex coupled with [Ru(η ⁵-C₅H₅)(MeCN)₃]⁺, providing another route to [Os₄Ru(CO)₁₃(η ⁵-C₅H₅)]^- (19). This anionic complex may also be coupled with [Ru(η⁶-C₆H ₆)(MeCN)₃]²⁺ affording [Os₄Ru(CO) ₁₃(η⁶-C₆H₆)] (21) which has also been structurally characterised.

Original language	English
Pages (from-to)	299-313
Number of pages	15
Journal	Inorganica Chimica Acta
Volume	350
DOIs	https://doi.org/10.1016/S0020-1693(02)01516-5
Publication status	Published - Jul 4 2003

Keywords

Arene
Carbonyl
Cluster
Crystal structures
Cyclopentadiene
Gold
Osmium
Ruthenium

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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Use of the cationic fragments [Ru(η⁵-C₅H ₅)(MeCN)₃]⁺ and [M(η⁶-C ₆H₅R)(MeCN)₃]⁺ (M=Os, Ru; R=H, Me) as ionic coupling reagents with the anions. / Al-Mandhary, Muna R.A.; Buntem, Radchada; Cathey, Christopher; Lewis, Jack; De Arellano, M. Carmen Ramirez; Shields, Gregory P.; Doherty, Cheryl L.; Raithby, Paul R.

In: Inorganica Chimica Acta, Vol. 350, 04.07.2003, p. 299-313.

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

Al-Mandhary, Muna R.A. ; Buntem, Radchada ; Cathey, Christopher ; Lewis, Jack ; De Arellano, M. Carmen Ramirez ; Shields, Gregory P. ; Doherty, Cheryl L. ; Raithby, Paul R. / Use of the cationic fragments [Ru(η⁵-C₅H ₅)(MeCN)₃]⁺ and [M(η⁶-C ₆H₅R)(MeCN)₃]⁺ (M=Os, Ru; R=H, Me) as ionic coupling reagents with the anions. In: Inorganica Chimica Acta. 2003 ; Vol. 350. pp. 299-313.

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title = "Use of the cationic fragments [Ru(η5-C5H 5)(MeCN)3]+ and [M(η6-C 6H5R)(MeCN)3]+ (M=Os, Ru; R=H, Me) as ionic coupling reagents with the anions",

abstract = "The cluster [H2Os4(CO)13] may be reduced with K/Ph2CO to generate an anion which reacts with [M(η 6-C6H5R)(MeCN)3]2+ (M=Os, Ru; R=H, Me) affording the capped clusters [H2Os4M(CO) 12(η6-C6H5R)] (M=Os, R=H (1); M=Ru, R=H (2); M=Os, R=Me (3)) with the arene ligand on one of the axial site of a trigonal bipyramid. The Os clusters 1 and 3 transform into the more stable equatorial isomers, 4 and 5, respectively, in 24 h. The structure of 5 has been confirmed by a single crystal X-ray diffraction study, and all the complexes have been characterised spectroscopically. The axial isomers may be carbonylated or hydrogenated to generate the edge-bridged tetrahedral clusters [H2Os4M(CO)13(η6-C 6H5R)] (M=Os, R=H (6); M=Ru, R=H (7); M=Os, R=Me (8)) and the known clusters [H4Os4M(CO)12(η 6-C6H6)] (M=Os (9); Ru (10)). The structure of 7 has been confirmed by an X-ray diffraction analysis. The axial isomer 1 reacts with PPh2Me to yield the addition product [H 2Os5(CO)12(η6-C 6H6)PPh2Me] (11), whereas the mixed osmium-ruthenium analogue undergoes a transformation to the 'spiked' tetrahedral [H3Os4Ru(CO)12(μ 3-σ,σ,η6-C6H 5)PPh2Me] (12). Deprotonation of the axial isomers 1 and 2 and subsequent reaction with [AuPPh3]+ yields [HOs 4M(CO)12(C6H6)(AuPPh3)] (M=Os (13); Ru (14)). As well as spectroscopic characterisation cluster, the structures of 11, 12 and 13 have been established by X-ray diffraction experiments. In a related series of reactions the cluster monoanion [Os 4(CO)13X]- (X=Cl (15), Br (16), I (17)) may be capped using the monocation [Ru(η5-C5H 5)(MeCN)3]+ affording [HOs4Ru(CO) 13(η5-C5H5)] (18), which is readily deprotonated and further capped with [AuPPh3]+ to afford the neutral cluster [Os4(CO)13Ru(η 5-C5H5)AuPPh3] (20). The structures of 15, 18 and 20 have been established crystallographically. The cluster anion [Os4(CO)13X]- may be reduced with K/Ph 2CO and the resulting anionic complex coupled with [Ru(η 5-C5H5)(MeCN)3]+, providing another route to [Os4Ru(CO)13(η 5-C5H5)]- (19). This anionic complex may also be coupled with [Ru(η6-C6H 6)(MeCN)3]2+ affording [Os4Ru(CO) 13(η6-C6H6)] (21) which has also been structurally characterised.",

keywords = "Arene, Carbonyl, Cluster, Crystal structures, Cyclopentadiene, Gold, Osmium, Ruthenium",

author = "Al-Mandhary, {Muna R.A.} and Radchada Buntem and Christopher Cathey and Jack Lewis and {De Arellano}, {M. Carmen Ramirez} and Shields, {Gregory P.} and Doherty, {Cheryl L.} and Raithby, {Paul R.}",

year = "2003",

month = jul,

day = "4",

doi = "10.1016/S0020-1693(02)01516-5",

language = "English",

volume = "350",

pages = "299--313",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier BV",

}

TY - JOUR

T1 - Use of the cationic fragments [Ru(η5-C5H 5)(MeCN)3]+ and [M(η6-C 6H5R)(MeCN)3]+ (M=Os, Ru; R=H, Me) as ionic coupling reagents with the anions

AU - Al-Mandhary, Muna R.A.

AU - Buntem, Radchada

AU - Cathey, Christopher

AU - Lewis, Jack

AU - De Arellano, M. Carmen Ramirez

AU - Shields, Gregory P.

AU - Doherty, Cheryl L.

AU - Raithby, Paul R.

PY - 2003/7/4

Y1 - 2003/7/4

N2 - The cluster [H2Os4(CO)13] may be reduced with K/Ph2CO to generate an anion which reacts with [M(η 6-C6H5R)(MeCN)3]2+ (M=Os, Ru; R=H, Me) affording the capped clusters [H2Os4M(CO) 12(η6-C6H5R)] (M=Os, R=H (1); M=Ru, R=H (2); M=Os, R=Me (3)) with the arene ligand on one of the axial site of a trigonal bipyramid. The Os clusters 1 and 3 transform into the more stable equatorial isomers, 4 and 5, respectively, in 24 h. The structure of 5 has been confirmed by a single crystal X-ray diffraction study, and all the complexes have been characterised spectroscopically. The axial isomers may be carbonylated or hydrogenated to generate the edge-bridged tetrahedral clusters [H2Os4M(CO)13(η6-C 6H5R)] (M=Os, R=H (6); M=Ru, R=H (7); M=Os, R=Me (8)) and the known clusters [H4Os4M(CO)12(η 6-C6H6)] (M=Os (9); Ru (10)). The structure of 7 has been confirmed by an X-ray diffraction analysis. The axial isomer 1 reacts with PPh2Me to yield the addition product [H 2Os5(CO)12(η6-C 6H6)PPh2Me] (11), whereas the mixed osmium-ruthenium analogue undergoes a transformation to the 'spiked' tetrahedral [H3Os4Ru(CO)12(μ 3-σ,σ,η6-C6H 5)PPh2Me] (12). Deprotonation of the axial isomers 1 and 2 and subsequent reaction with [AuPPh3]+ yields [HOs 4M(CO)12(C6H6)(AuPPh3)] (M=Os (13); Ru (14)). As well as spectroscopic characterisation cluster, the structures of 11, 12 and 13 have been established by X-ray diffraction experiments. In a related series of reactions the cluster monoanion [Os 4(CO)13X]- (X=Cl (15), Br (16), I (17)) may be capped using the monocation [Ru(η5-C5H 5)(MeCN)3]+ affording [HOs4Ru(CO) 13(η5-C5H5)] (18), which is readily deprotonated and further capped with [AuPPh3]+ to afford the neutral cluster [Os4(CO)13Ru(η 5-C5H5)AuPPh3] (20). The structures of 15, 18 and 20 have been established crystallographically. The cluster anion [Os4(CO)13X]- may be reduced with K/Ph 2CO and the resulting anionic complex coupled with [Ru(η 5-C5H5)(MeCN)3]+, providing another route to [Os4Ru(CO)13(η 5-C5H5)]- (19). This anionic complex may also be coupled with [Ru(η6-C6H 6)(MeCN)3]2+ affording [Os4Ru(CO) 13(η6-C6H6)] (21) which has also been structurally characterised.

AB - The cluster [H2Os4(CO)13] may be reduced with K/Ph2CO to generate an anion which reacts with [M(η 6-C6H5R)(MeCN)3]2+ (M=Os, Ru; R=H, Me) affording the capped clusters [H2Os4M(CO) 12(η6-C6H5R)] (M=Os, R=H (1); M=Ru, R=H (2); M=Os, R=Me (3)) with the arene ligand on one of the axial site of a trigonal bipyramid. The Os clusters 1 and 3 transform into the more stable equatorial isomers, 4 and 5, respectively, in 24 h. The structure of 5 has been confirmed by a single crystal X-ray diffraction study, and all the complexes have been characterised spectroscopically. The axial isomers may be carbonylated or hydrogenated to generate the edge-bridged tetrahedral clusters [H2Os4M(CO)13(η6-C 6H5R)] (M=Os, R=H (6); M=Ru, R=H (7); M=Os, R=Me (8)) and the known clusters [H4Os4M(CO)12(η 6-C6H6)] (M=Os (9); Ru (10)). The structure of 7 has been confirmed by an X-ray diffraction analysis. The axial isomer 1 reacts with PPh2Me to yield the addition product [H 2Os5(CO)12(η6-C 6H6)PPh2Me] (11), whereas the mixed osmium-ruthenium analogue undergoes a transformation to the 'spiked' tetrahedral [H3Os4Ru(CO)12(μ 3-σ,σ,η6-C6H 5)PPh2Me] (12). Deprotonation of the axial isomers 1 and 2 and subsequent reaction with [AuPPh3]+ yields [HOs 4M(CO)12(C6H6)(AuPPh3)] (M=Os (13); Ru (14)). As well as spectroscopic characterisation cluster, the structures of 11, 12 and 13 have been established by X-ray diffraction experiments. In a related series of reactions the cluster monoanion [Os 4(CO)13X]- (X=Cl (15), Br (16), I (17)) may be capped using the monocation [Ru(η5-C5H 5)(MeCN)3]+ affording [HOs4Ru(CO) 13(η5-C5H5)] (18), which is readily deprotonated and further capped with [AuPPh3]+ to afford the neutral cluster [Os4(CO)13Ru(η 5-C5H5)AuPPh3] (20). The structures of 15, 18 and 20 have been established crystallographically. The cluster anion [Os4(CO)13X]- may be reduced with K/Ph 2CO and the resulting anionic complex coupled with [Ru(η 5-C5H5)(MeCN)3]+, providing another route to [Os4Ru(CO)13(η 5-C5H5)]- (19). This anionic complex may also be coupled with [Ru(η6-C6H 6)(MeCN)3]2+ affording [Os4Ru(CO) 13(η6-C6H6)] (21) which has also been structurally characterised.

KW - Arene

KW - Carbonyl

KW - Cluster

KW - Crystal structures

KW - Cyclopentadiene

KW - Gold

KW - Osmium

KW - Ruthenium

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U2 - 10.1016/S0020-1693(02)01516-5

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M3 - Article

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JO - Inorganica Chimica Acta

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