Use of the cationic fragments [Ru(η5-C5H 5) (MeCN)3]+ and [M(η6-C 6H5R)(MeCN)3]+

Muna R.A. Al-Mandhary; Radchada Buntem; Cheryl L. Doherty; Andrew J. Edwards; John F. Gallagher; Jack Lewis; Chi Keung Li; Paul R. Raithby; M. Carmen Ramirez De Arellano; Gregory P. Shields

doi:10.1007/s10876-005-4402-2

Use of the cationic fragments [Ru(η⁵-C₅H ₅) (MeCN)₃]⁺ and [M(η⁶-C ₆H₅R)(MeCN)₃]⁺

Muna R.A. Al-Mandhary, Radchada Buntem, Cheryl L. Doherty, Andrew J. Edwards, John F. Gallagher, Jack Lewis, Chi Keung Li, Paul R. Raithby^*, M. Carmen Ramirez De Arellano, Gregory P. Shields

^*Corresponding author for this work

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

5 Citations (Scopus)

Abstract

The clusters [H₂Os₄M(CO)₁₂η ⁶-C₆H₆)] (M=Os, Ru) may be deprotonated to generate anions [Os₄M(CO)₁₂(η⁶-C ₆H₆)]^2- which react with [M′η ⁶-C₆H₅R) (MeCN)₃] ²⁺(M′=Os, Ru; R=H, Me) to give the bicapped tetrahedral clusters [Os₄(CO)₁₂MM′(η⁶-C ₆H₅R)₂]. Whereas [Os₄(CO) ₁₂M₂η⁶-C₆H₆) ₂] (M=Os, Ru) have one M(η⁶-C₆H ₆) unit in a site connected to three other metals, {3}, and one in a site connected to four other metals, {4}, [Os₄(CO) ₁₂OsRu(η⁶-C₆H₆)₂] has the Ru(η⁶-C₆H₆) unit in the {3} site irrespective of whether the Os or Ru anion is capped. Coupling of these anions with Au₂dppm yields [Os₄M(CO)₁₂(η ⁶-C₆H₆)(Au₂dppm)] (M=Os, Ru), which have the arene ligand in the axial site of a trigonal bipyramid and the digold unit capping two faces. Reduction of [H₂Os₅(CO) ₁₅] with K/Ph₂CO and coupling with [Ru(η⁵- C₅H₅)(MeCN)₃]²⁺yields the monoanion [Os₅(CO)₁₅Ru(η⁵-C₅H ₅)]^- which reacts with [AuPPh₃]⁺ generating [Os₅(CO)₁₅Ru(η⁵-C ₅H₅)(AuPPh₃)] with the "Ru(C ₅H₅)" unit in the terminal {3} site.

Original language	English
Pages (from-to)	127-150
Number of pages	24
Journal	Journal of Cluster Science
Volume	16
Issue number	2
DOIs	https://doi.org/10.1007/s10876-005-4402-2
Publication status	Published - Jun 2005
Externally published	Yes

Keywords

Carbonyl cluster
Cyclopentadienyl
Gold
Osmium
Ruthenium
X-ray crystal structures

ASJC Scopus subject areas

Biochemistry
Chemistry(all)
Materials Science(all)
Condensed Matter Physics

Access to Document

10.1007/s10876-005-4402-2

Cite this

Use of the cationic fragments [Ru(η⁵-C₅H ₅) (MeCN)₃]⁺ and [M(η⁶-C ₆H₅R)(MeCN)₃]⁺. / Al-Mandhary, Muna R.A.; Buntem, Radchada; Doherty, Cheryl L.; Edwards, Andrew J.; Gallagher, John F.; Lewis, Jack; Li, Chi Keung; Raithby, Paul R.; Ramirez De Arellano, M. Carmen; Shields, Gregory P.

In: Journal of Cluster Science, Vol. 16, No. 2, 06.2005, p. 127-150.

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

@article{1f3f29820a5c440491e0e5f37aac8ca0,

title = "Use of the cationic fragments [Ru(η5-C5H 5) (MeCN)3]+ and [M(η6-C 6H5R)(MeCN)3]+",

abstract = "The clusters [H2Os4M(CO)12η 6-C6H6)] (M=Os, Ru) may be deprotonated to generate anions [Os4M(CO)12(η6-C 6H6)]2- which react with [M′η 6-C6H5R) (MeCN)3] 2+(M′=Os, Ru; R=H, Me) to give the bicapped tetrahedral clusters [Os4(CO)12MM′(η6-C 6H5R)2]. Whereas [Os4(CO) 12M2η6-C6H6) 2] (M=Os, Ru) have one M(η6-C6H 6) unit in a site connected to three other metals, {3}, and one in a site connected to four other metals, {4}, [Os4(CO) 12OsRu(η6-C6H6)2] has the Ru(η6-C6H6) unit in the {3} site irrespective of whether the Os or Ru anion is capped. Coupling of these anions with Au2dppm yields [Os4M(CO)12(η 6-C6H6)(Au2dppm)] (M=Os, Ru), which have the arene ligand in the axial site of a trigonal bipyramid and the digold unit capping two faces. Reduction of [H2Os5(CO) 15] with K/Ph2CO and coupling with [Ru(η5- C5H5)(MeCN)3]2+yields the monoanion [Os5(CO)15Ru(η5-C5H 5)]- which reacts with [AuPPh3]+ generating [Os5(CO)15Ru(η5-C 5H5)(AuPPh3)] with the {"}Ru(C 5H5){"} unit in the terminal {3} site.",

keywords = "Carbonyl cluster, Cyclopentadienyl, Gold, Osmium, Ruthenium, X-ray crystal structures",

author = "Al-Mandhary, {Muna R.A.} and Radchada Buntem and Doherty, {Cheryl L.} and Edwards, {Andrew J.} and Gallagher, {John F.} and Jack Lewis and Li, {Chi Keung} and Raithby, {Paul R.} and {Ramirez De Arellano}, {M. Carmen} and Shields, {Gregory P.}",

note = "Funding Information: The authors thank The Government of the Sultanate of Oman (M.R.A.A), The Overseas Research Students Awards (M.R.A.A.), The Croucher Foundation (C.-K.L.), The Cambridge Thai Trust (R.B.), the E.P.S.R.C (C.L.D., A.J.E., G.P.S) and the Cambridge Crystallographic Data Centre (G.P.S) for funding, the EU for Human Capital and Mobility Grants (M.C.R. de A., J. F. G.) and Johnson Matthey PLC for the generous loan of osmium and ruthenium salts.",

year = "2005",

month = jun,

doi = "10.1007/s10876-005-4402-2",

language = "English",

volume = "16",

pages = "127--150",

journal = "Journal of Cluster Science",

issn = "1040-7278",

publisher = "Springer New York",

number = "2",

}

TY - JOUR

T1 - Use of the cationic fragments [Ru(η5-C5H 5) (MeCN)3]+ and [M(η6-C 6H5R)(MeCN)3]+

AU - Al-Mandhary, Muna R.A.

AU - Buntem, Radchada

AU - Doherty, Cheryl L.

AU - Edwards, Andrew J.

AU - Gallagher, John F.

AU - Lewis, Jack

AU - Li, Chi Keung

AU - Raithby, Paul R.

AU - Ramirez De Arellano, M. Carmen

AU - Shields, Gregory P.

N1 - Funding Information: The authors thank The Government of the Sultanate of Oman (M.R.A.A), The Overseas Research Students Awards (M.R.A.A.), The Croucher Foundation (C.-K.L.), The Cambridge Thai Trust (R.B.), the E.P.S.R.C (C.L.D., A.J.E., G.P.S) and the Cambridge Crystallographic Data Centre (G.P.S) for funding, the EU for Human Capital and Mobility Grants (M.C.R. de A., J. F. G.) and Johnson Matthey PLC for the generous loan of osmium and ruthenium salts.

PY - 2005/6

Y1 - 2005/6

N2 - The clusters [H2Os4M(CO)12η 6-C6H6)] (M=Os, Ru) may be deprotonated to generate anions [Os4M(CO)12(η6-C 6H6)]2- which react with [M′η 6-C6H5R) (MeCN)3] 2+(M′=Os, Ru; R=H, Me) to give the bicapped tetrahedral clusters [Os4(CO)12MM′(η6-C 6H5R)2]. Whereas [Os4(CO) 12M2η6-C6H6) 2] (M=Os, Ru) have one M(η6-C6H 6) unit in a site connected to three other metals, {3}, and one in a site connected to four other metals, {4}, [Os4(CO) 12OsRu(η6-C6H6)2] has the Ru(η6-C6H6) unit in the {3} site irrespective of whether the Os or Ru anion is capped. Coupling of these anions with Au2dppm yields [Os4M(CO)12(η 6-C6H6)(Au2dppm)] (M=Os, Ru), which have the arene ligand in the axial site of a trigonal bipyramid and the digold unit capping two faces. Reduction of [H2Os5(CO) 15] with K/Ph2CO and coupling with [Ru(η5- C5H5)(MeCN)3]2+yields the monoanion [Os5(CO)15Ru(η5-C5H 5)]- which reacts with [AuPPh3]+ generating [Os5(CO)15Ru(η5-C 5H5)(AuPPh3)] with the "Ru(C 5H5)" unit in the terminal {3} site.

AB - The clusters [H2Os4M(CO)12η 6-C6H6)] (M=Os, Ru) may be deprotonated to generate anions [Os4M(CO)12(η6-C 6H6)]2- which react with [M′η 6-C6H5R) (MeCN)3] 2+(M′=Os, Ru; R=H, Me) to give the bicapped tetrahedral clusters [Os4(CO)12MM′(η6-C 6H5R)2]. Whereas [Os4(CO) 12M2η6-C6H6) 2] (M=Os, Ru) have one M(η6-C6H 6) unit in a site connected to three other metals, {3}, and one in a site connected to four other metals, {4}, [Os4(CO) 12OsRu(η6-C6H6)2] has the Ru(η6-C6H6) unit in the {3} site irrespective of whether the Os or Ru anion is capped. Coupling of these anions with Au2dppm yields [Os4M(CO)12(η 6-C6H6)(Au2dppm)] (M=Os, Ru), which have the arene ligand in the axial site of a trigonal bipyramid and the digold unit capping two faces. Reduction of [H2Os5(CO) 15] with K/Ph2CO and coupling with [Ru(η5- C5H5)(MeCN)3]2+yields the monoanion [Os5(CO)15Ru(η5-C5H 5)]- which reacts with [AuPPh3]+ generating [Os5(CO)15Ru(η5-C 5H5)(AuPPh3)] with the "Ru(C 5H5)" unit in the terminal {3} site.

KW - Carbonyl cluster

KW - Cyclopentadienyl

KW - Gold

KW - Osmium

KW - Ruthenium

KW - X-ray crystal structures

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U2 - 10.1007/s10876-005-4402-2

DO - 10.1007/s10876-005-4402-2

M3 - Article

AN - SCOPUS:22044449477

VL - 16

SP - 127

EP - 150

JO - Journal of Cluster Science

JF - Journal of Cluster Science

SN - 1040-7278

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