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

Research output: Contribution to journal › Article

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 languageEnglish
Pages (from-to)299-313
Number of pages15
JournalInorganica Chimica Acta
Volume350
DOIs
Publication statusPublished - Jul 4 2003

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Isomers
Anions
reagents
Negative ions
fragments
anions
Osmium
X ray diffraction
Deprotonation
Ruthenium
X ray diffraction analysis
Ligands
Single crystals
isomers
Experiments
diffraction
x rays
osmium
ruthenium

Keywords

  • Arene
  • Carbonyl
  • Cluster
  • Crystal structures
  • Cyclopentadiene
  • Gold
  • Osmium
  • Ruthenium

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

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

Al-Mandhary, MRA, Buntem, R, Cathey, C, Lewis, J, De Arellano, MCR, Shields, GP, Doherty, CL & Raithby, PR 2003, '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', Inorganica Chimica Acta, vol. 350, pp. 299-313. https://doi.org/10.1016/S0020-1693(02)01516-5
Al-Mandhary MRA, Buntem R, Cathey C, Lewis J, De Arellano MCR, Shields GP et al. 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. Inorganica Chimica Acta. 2003 Jul 4;350:299-313. https://doi.org/10.1016/S0020-1693(02)01516-5
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.}",
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pages = "299--313",
journal = "Inorganica Chimica Acta",
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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

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

M3 - Article

AN - SCOPUS:0142184861

VL - 350

SP - 299

EP - 313

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

ER -

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