Cluster chemistry

Bruce, Michael I.; Liddell, Michael J.; Hughes, Caroline A.; Patrick, Jennifer M.; Skelton, Brian W.; White, Allan H.

doi:10.1016/0022-328x(88)80281-x

Cited by 114 publications

(71 citation statements)

References 7 publications

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“…The Ru-P distance of 2.369(1) A lies in the range 2.24 to 2.43 noted by Bruce and co-workers (47). A plot of Ru-P distance against ligand cone angle results in a smooth curve (48) but based on a cone angle of 156", the observed Ru-P distance is shorter than would be predicted.…”

Section: Structural Studiesmentioning

confidence: 54%

“…Otherwise the structure shown in Fig. 1 resembles other known R U~( C O )~ I L derivatives in that the metal cluster skeleton is distorted from the D,,, symmetry found in R U~( C O )~~, principally by rotation of the Ru(CO)~ unit (46,47).…”

Section: Structural Studiesmentioning

confidence: 88%

“…The longer Ru(2)-Ru(2') bond, 2.9284(5) A , is situated cis to two Ru-P bonds (see (ii) above) and this length is greater than the longest bond in R U~( C O )~ 1(PFcPh2), (2.9000(6) A) and in fact, is longer than that found in any R u~( C O ) ,~-~L , , ( n = 1-4) derivative3 (46,47). This lengthening is probably not entirely due to a repulsive cis effect as the Ru-Ru bond length of other R U~ ( C O ) (52), and to reiterate dppf, 2.9284(5), 2.8600(4), 2.8600(4) A.…”

Section: Structural Studiesmentioning

confidence: 88%

“…1 (21,46,47); those of relevance to the structure of R U , ( C O )~~ (PFcPh,) are as follows: (i) P-ligands coordinate equatorial sites, (ii) the Ru-Ru bond cis to P-ligands is the longest of the three separations, and (iii) bonds from axial CO groups to Ru are generally longer than those from equatorial CO groups except when the latter are cis to a P-ligand. Taking these in turn (i) is certainly true, as is (ii).…”

Section: Structural Studiesmentioning

confidence: 99%

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Some reactions of ferrocenyl phosphines with M₃(CO)₁₂ (M = Fe, Ru). The structures of Ru₃(CO)₁₁(PFcPh₂) and Ru₃(CO)₁₀{(PPh₂-η-C₅H₄)₂Fe}

Chacon¹,

Cullen²,

Bruce³

et al. 1990

Can. J. Chem.

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Tertiary phosphine substituted metal carbonyl complexes are generally very well known (1) although there have been only a few studies in this area involving ferrocenylphosphines such as PFc,Ph,-,, n = 1-3 (2-8) (FcH = Fe(q-CSH5)2), and 1,l'-disubstituted ferrocene derivatives such as dppf, l,lf-bis(dipheny1phosphino)ferrocene (2,9,10). Phosphine derivatives are generally prepared by direct reaction of the phosphine with the metal carbonyl. Sometimes, and especially in the case of Fe3(C0)12, cluster breakdown is found so that the isolated products are phosphine derivatives of mononuclear carbonyls, e.g. (Fe(C0)4(PR3) and Fe(C0)3(PR3)2 (3,5, 8, 1 1 -16). Reactions of this type involving R u~( C O )~~ usually afford trinuclear products (17)(18)(19)(20). Photosubstitution of R u~( C O )~~ seems to occur largely from higher energy states whereas photofragmentation involves the lowest excited state (20). The use of the radical anion, sodium diphenylketyl, as a catalyst has recently greatly facilitated the preparation of a wide range of derivatives Ru3(CO),,-,L,, n = 1-4, because the reactions are essentially stoichiometric (21). The method is also useful for the synthesis of derivatives of Fe3(C0)12. Salts of the bis(tripheny1phos-phine)iminium ion, ppn+, are also effective catalysts (22).In view of the success in trapping a benzyne fragment on a metal cluster from reactions of arylphosphines with M3(CO),2 'Author to whom correspondence may be addressed.(M = Ru, 0 s ) (23-25) directly or stepwise, we have initiated a study of the corresponding reactions of ferrocenylphosphines in the hope that this will lead to the trapping of a ferrocyne fragment. The present paper describes the synthesis of some derivatives of Fe3(C0)12 and R U~( C O )~~, because of our interest in their pyrolysis products, and the crystal structures of R u~( C O )~ I(PF~Ph2) and Ru3(CO) ,o(p-dppf). The thermal decomposition of R U~( C O )~, , ( P F C P~~)~ to a benzyne complex has been reported (25). Experimental sectionReactions were carried out in a nitrogen atmosphere by using standard Schlenk procedures. Solvents were dried and distilled before use. Separation of products was usually achieved by column chromatography on Florisil or neutral alumina (activity I) by using petroleum ether (35-60°C bp fraction)/diethyl ether mixtures as eluent. I H NMR spectra were recorded from CDC13 solutions by using Bruker WH400 or WP80 and Varian XL300 instruments. Infrared spectra, usually of C6H12 solutions, were run on a Bowman Fourier Transform or a Perkin Elmer 589 spectrometer. Mass spectra were obtained from a Kratos MS 50 instrument; only peaks with high m / e values are listed and electron impact ionization was used unless otherwise stated. Elemental analyses were determined by Mr. P. Borda of the Chemistry Department, University of British Columbia. Melting points were measured by using a Kofler microheating stage and are uncorrected. A Hanovia lOOW lamp (903A-1) was used for UV irradiations. To minimize

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Section: Structural Studiesmentioning

confidence: 54%

Section: Structural Studiesmentioning

confidence: 88%

Section: Structural Studiesmentioning

confidence: 88%

Section: Structural Studiesmentioning

confidence: 99%

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Some reactions of ferrocenyl phosphines with M₃(CO)₁₂ (M = Fe, Ru). The structures of Ru₃(CO)₁₁(PFcPh₂) and Ru₃(CO)₁₀{(PPh₂-η-C₅H₄)₂Fe}

Chacon¹,

Cullen²,

Bruce³

et al. 1990

Can. J. Chem.

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“…No hydrido signals could be detected, indicating that ortho-metallation had not taken place. The room-temperature 31 P{ 1 H} NMR spectra show a singlet at δ = -16.2 ppm for 1, a signal at δ = -17.3 (br.) ppm and doublet at δ = -32.7 (J P-P = 6.4 Hz) ppm for 2 (vide infra), and a singlet at δ = -17.2 ppm for 3.…”

Section: Thermal Treatment Of [Os 3 (Co) 12 ] With Ph 2 P(c 4 H 3 S)mentioning

confidence: 98%

Syntheses and Fluxional Processes of Diphenyl(2‐thienyl)phosphane Derivatives of Triosmium Clusters

et al. 2006

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Thermal treatment of [Os3(CO)12] with diphenyl(2‐thienyl)phosphane, Ph2P(C4H3S), results in the formation of [Os3(CO)12–x{Ph2P(C4H3S)}x] (x = 1–3, 1–3), but no C–H bond activation was observed. Reaction of [H2Os3(CO)10] with diphenyl(2‐thienyl)phosphane at ambient temperature affords [HOs3(μ‐H)(CO)10{Ph2P(C4H3S)}] (4), but when the samereaction is repeated at elevated temperatures, the cyclometallated species [(μ‐H)Os3(CO)9{μ3‐Ph2P(C4H2S)}] (5) and[(μ‐H)Os3(CO)8{μ3‐Ph2P(C4H2S)}{Ph2P(C4H3S)}] (6) are formed. In addition, two more products, tentatively assigned as [(μ‐H)Os3(CO)6{μ3‐Ph2P(C4H2S)}{μ‐Ph2P(C4H3S)}{Ph2P(C4H3S)}] (7) and [(μ‐H)Os3(CO)7{μ‐Ph2P(C4H2S)}{μ‐Ph2P(C4H3S)}{Ph2P(C4H3S)}] (8) are obtained. The dynamic behaviours of 2, 5 and 6 have been studied by variable‐temperature (VT) 1H and 31P{1H} NMR spectroscopy. The VT 31P{1H} NMR spectra of [Os3(CO)10{Ph2P(C4H3S)}2] (2) demonstrate that a mixture of two isomers, which are in rapid exchange at room temperature, is present and that the less common cis‐trans isomer, whose structure has been determined by X‐ray crystallography, is favoured for this cluster. The VT 1H NMR spectra of 5 indicate the presence of two isomers which are proposed to arise from an oscillation of the σ,η2‐vinyl group of the thienyl moiety between two metal atoms. A similar fluxional process is proposed to occur in 6 and the assignment of the room‐temperature structure(s) of this cluster was confirmed by 1H‐187Os 2D HMQC spectroscopy. In addition to 2, the solid‐state structures of 3, 5 and 6 have been determined by X‐ray crystallography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Structure and Dynamics in Metal Carbonyl Clusters: NMR, EXAFS and Crystallographic Studies

Farrugia¹,

Orpen²

1999

Metal Clusters in Chemistry

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Cluster chemistry

Cited by 114 publications

References 7 publications

Some reactions of ferrocenyl phosphines with M₃(CO)₁₂ (M = Fe, Ru). The structures of Ru₃(CO)₁₁(PFcPh₂) and Ru₃(CO)₁₀{(PPh₂-η-C₅H₄)₂Fe}

Some reactions of ferrocenyl phosphines with M₃(CO)₁₂ (M = Fe, Ru). The structures of Ru₃(CO)₁₁(PFcPh₂) and Ru₃(CO)₁₀{(PPh₂-η-C₅H₄)₂Fe}

Syntheses and Fluxional Processes of Diphenyl(2‐thienyl)phosphane Derivatives of Triosmium Clusters

Structure and Dynamics in Metal Carbonyl Clusters: NMR, EXAFS and Crystallographic Studies

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Cluster chemistry

Cited by 114 publications

References 7 publications

Some reactions of ferrocenyl phosphines with M3(CO)12 (M = Fe, Ru). The structures of Ru3(CO)11(PFcPh2) and Ru3(CO)10{(PPh2-η-C5H4)2Fe}

Some reactions of ferrocenyl phosphines with M3(CO)12 (M = Fe, Ru). The structures of Ru3(CO)11(PFcPh2) and Ru3(CO)10{(PPh2-η-C5H4)2Fe}

Syntheses and Fluxional Processes of Diphenyl(2‐thienyl)phosphane Derivatives of Triosmium Clusters

Structure and Dynamics in Metal Carbonyl Clusters: NMR, EXAFS and Crystallographic Studies

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Some reactions of ferrocenyl phosphines with M₃(CO)₁₂ (M = Fe, Ru). The structures of Ru₃(CO)₁₁(PFcPh₂) and Ru₃(CO)₁₀{(PPh₂-η-C₅H₄)₂Fe}

Some reactions of ferrocenyl phosphines with M₃(CO)₁₂ (M = Fe, Ru). The structures of Ru₃(CO)₁₁(PFcPh₂) and Ru₃(CO)₁₀{(PPh₂-η-C₅H₄)₂Fe}