Reactivity and catalytic activity of heteronuclear clusters.  1.  Fluxional decapping of the heterometallic moiety in H3Ru4(CO)12MPR3 (M = Au, Cu) and the crystal structure of H3Ru4(CO)12AuPPh3

Evans, John; Street, Andrew C.; Webster, Michael

doi:10.1021/om00147a018

Cited by 18 publications

(9 citation statements)

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“…Behavior of Adducts 2 − 4 in Solution. The addition of a good donor molecule such as PPh 3 to CH 2 Cl 2 solutions of the adducts 2 − 4 restored the starting anion 1 , according to eq 8. − In agreement with previous literature data,31b the complete conversion of the different adducts into 1 required different amounts of phosphine: 1 equiv of PPh 3 was sufficient for the gold adduct 3 and 2 equiv was necessary for the copper derivative 4 , while in the case of the silver adduct 2 a still higher amount was required, due to the formations of mixtures of the [Ag(PPh 3 ) 3 ] + and [Ag(PPh 3 ) 4 ] + cations (see Experimental Section).…”

Section: Resultssupporting

confidence: 86%

“…The [M(PPh 3 )] + cations exhibit different labilities: the gold derivative is inert even in acetone, while the copper and silver adducts are labile (on the NMR time scale) also in CH 2 Cl 2 , at room temperature. Examples of intermolecular exchange of [M(PPh 3 )] + moieties in solution have already been reported, and also the fact that gold complexes tend to be less dynamic has been previously pointed out. 31b, …”

Section: Resultsmentioning

confidence: 82%

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Synthesis, Solid-State Structure and Solution Behavior of Hydrido-Bridged Adducts between the Group 11 [M(PPh₃)]⁺Cations and the Triangular Cluster Anion [Re₃(μ-H)₄(CO)₉(PPh₃)]^-

Beringhelli¹,

D’Alfonso²,

Garavaglia³

et al. 2002

Organometallics

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The reactions of the unsaturated anion [Re 3 (µ-H) 4 (CO) 9 (PPh 3 )] -(1) with the metallic Lewis acids [M(PPh 3 )] + (M ) Cu, Ag, Au) afford the addition derivatives [Re 3 {µ-M(PPh 3 )}(µ 3 -H)-(µ-H) 3 (CO) 9 (PPh 3 )], which have been characterized in solution and in the solid state, by X-ray analysis. The copper derivative is obtained also by reaction of [Re 3 (µ-H) 3 (µ 3 -H)(CO) 9 ] -(as the [Re(CO) 3 (Me 2 CO) 3 ] + salt) with [Cu(PPh 3 ) 2 NO 3 ]. Treatment with PPh 3 extrudes the [M(PPh 3 )] + groups, restoring the starting anion 1. Solid-state structures of the adducts show a butterfly Re 3 M metal skeleton with one hydride bridging the Re 2 M face and three hydrides spanning the three Re-Re edges. The interaction of the [M(PPh 3 )] + cation with 1 leads only to a minor structural perturbation of the unsaturated Re 2 (µ-H) 2 moiety. The solid-state structure is maintained in nondonor solvents, while in acetone partial (Au, Ag) or complete (Cu) reversible ionic dissociation of the adducts is observed, affording 1 and solvated [M(PPh 3 )] + cations. Experiments performed in different solvents show that the donor power and not the dielectric constant is the key factor responsible for dissociation. For the silver adduct the dissociation in acetone is fast on the NMR time scale. The exchange between 1 and the silver or copper (but not gold) adducts occurs even in CD 2 Cl 2 .

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Section: Resultssupporting

confidence: 86%

Section: Resultsmentioning

confidence: 82%

Synthesis, Solid-State Structure and Solution Behavior of Hydrido-Bridged Adducts between the Group 11 [M(PPh₃)]⁺Cations and the Triangular Cluster Anion [Re₃(μ-H)₄(CO)₉(PPh₃)]^-

Beringhelli¹,

D’Alfonso²,

Garavaglia³

et al. 2002

Organometallics

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“…The general experimental procedures were as described in ref. 1, with the additional feature of fast atom bombardment mass spectrometry (FAB-MS) using a VG 70-250SE mass spectrometer and rn-nitrobenzyl alcohol as the matrix. The following compounds were prepared by established methods: ),(p3-PPh)] was prepared by the method described in ref.…”

Section: Methodsmentioning

confidence: 67%

Reactivity of [Ru₃H₂(CO)₉(µ₃-COMe){M(PPh₃)}](M = Cu, Ag or Au) and [Ru₃H(CO)₉(µ₃-PPh){Ag(PPh₃)}] with PPh₃

Evans¹,

Stroud²

1991

J. Chem. Soc., Dalton Trans.

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Addition of PPh, to [Ru,H,(CO),(p,-COMe){Cu( PPh,)}] 1 results in rapid heteronuclear decapping to form the anion [Ru,H,(CO),(p,-COMe)]-. A similar reaction occurs for the silver analogue 2 with excess of PPh,. However a 1 : 1 reaction mixture affords [Ag(PPh,),] [{Ru,H,(CO),(~,-COM~)}~A~] 5, which is stable in solution at low temperatures. NMR evidence is consistent with the anion having C, symmetry in which an approximately tetrahedrally co-ordinated silver centre links the two triruthenium clusters by edge bridging to each cluster. Reaction of [Ru,H(CO),(p,-PPh){Ag( PPh,)}] 4 with PPh, (1 :1) affords an equilibrium mixture (at 173 K) of [Ru,H(CO),(p,-PPh)]-, 4, [Ag(PPh,),]+ (n = 3 and 4) and [{Ru,H(CO),(p,-PPh)},Ag] -. All these reactions are faster than the carbonyl substitution reactions which occur at room temperature.

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“…A structural diversity of heterodimetallic and -trimetallic cores was observed for the pentanuclear species containing Au-Fe [296][297][298][299][300][301][302][303][304][305][306][307][308][309], Au-Ru [267,272,[310][311][312][313][314][315][316][317][318][319][320][321][322][323][324][325] and Au-Os [326][327][328][329][330][331][332][333][334][335]. A (Ph 3 P)Au unit can bridge in a m 3 -fashion a face of a tetrahedral heterodimetallic (Fe 2 Ir 2 , Fe 2 Rh 2 , Ru 2 Rh 2 , Ru 3 Rh, Ru 3 Co) core [296,297,310,311,315] [311]…”

Section: The Trimetallic Complex [Net 4 ][(Ph 3 P)aufe(co) 4 W(co) 5 mentioning

confidence: 99%

“…A (Ph 3 P)Au unit can bridge in a m 3 -fashion a face of a tetrahedral heterodimetallic (Fe 2 Ir 2 , Fe 2 Rh 2 , Ru 2 Rh 2 , Ru 3 Rh, Ru 3 Co) core [296,297,310,311,315] [311]. For Ru and Os clusters a common pattern is the edge-bridging of a (R 3 P)Au fragment to a homonuclear M 4 (M ¼ Ru [312], Os [326][327][328][329][330]) or heteronuclear M 3 W (M ¼ Ru [313], Os [331]), Ru 3 Co [315] and Os 3 Ni [332], for example, in (Ph 3 P)AuRu 3 W(h 5 -Cp)(m 3 -H)(m-H) (CO) 11 [327]. For clusters with an Au 2 M 3 core (M ¼ Fe [298][299][300], Ru [267,314,[316][317][318]) the distorted trigonal bipyramidal geometry can be considered as arising from a butterfly AuM 3 fragment m 4 -bridged by a second Au atom, for example [(Ph 3 P)Au] 2 An edge-bridged (R 3 P)Au unit was also found in pentanuclear clusters in which all four metal atoms of the butterfly tetrametallic core are coordinated by a carbon [301,302] or a nitrogen [303,321] atom.…”

Section: The Trimetallic Complex [Net 4 ][(Ph 3 P)aufe(co) 4 W(co) 5 mentioning

confidence: 99%

Gold–Heterometal Interactions and Bonds

Silvestru

2008

Modern Supramolecular Gold Chemistry

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Reactivity and catalytic activity of heteronuclear clusters. 1. Fluxional decapping of the heterometallic moiety in H3Ru4(CO)12MPR3 (M = Au, Cu) and the crystal structure of H3Ru4(CO)12AuPPh3

Cited by 18 publications

References 0 publications

Synthesis, Solid-State Structure and Solution Behavior of Hydrido-Bridged Adducts between the Group 11 [M(PPh₃)]⁺Cations and the Triangular Cluster Anion [Re₃(μ-H)₄(CO)₉(PPh₃)]^-

Synthesis, Solid-State Structure and Solution Behavior of Hydrido-Bridged Adducts between the Group 11 [M(PPh₃)]⁺Cations and the Triangular Cluster Anion [Re₃(μ-H)₄(CO)₉(PPh₃)]^-

Reactivity of [Ru₃H₂(CO)₉(µ₃-COMe){M(PPh₃)}](M = Cu, Ag or Au) and [Ru₃H(CO)₉(µ₃-PPh){Ag(PPh₃)}] with PPh₃

Gold–Heterometal Interactions and Bonds

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Reactivity and catalytic activity of heteronuclear clusters. 1. Fluxional decapping of the heterometallic moiety in H3Ru4(CO)12MPR3 (M = Au, Cu) and the crystal structure of H3Ru4(CO)12AuPPh3

Cited by 18 publications

References 0 publications

Synthesis, Solid-State Structure and Solution Behavior of Hydrido-Bridged Adducts between the Group 11 [M(PPh3)]+Cations and the Triangular Cluster Anion [Re3(μ-H)4(CO)9(PPh3)]-

Synthesis, Solid-State Structure and Solution Behavior of Hydrido-Bridged Adducts between the Group 11 [M(PPh3)]+Cations and the Triangular Cluster Anion [Re3(μ-H)4(CO)9(PPh3)]-

Reactivity of [Ru3H2(CO)9(µ3-COMe){M(PPh3)}](M = Cu, Ag or Au) and [Ru3H(CO)9(µ3-PPh){Ag(PPh3)}] with PPh3

Gold–Heterometal Interactions and Bonds

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Synthesis, Solid-State Structure and Solution Behavior of Hydrido-Bridged Adducts between the Group 11 [M(PPh₃)]⁺Cations and the Triangular Cluster Anion [Re₃(μ-H)₄(CO)₉(PPh₃)]^-

Synthesis, Solid-State Structure and Solution Behavior of Hydrido-Bridged Adducts between the Group 11 [M(PPh₃)]⁺Cations and the Triangular Cluster Anion [Re₃(μ-H)₄(CO)₉(PPh₃)]^-

Reactivity of [Ru₃H₂(CO)₉(µ₃-COMe){M(PPh₃)}](M = Cu, Ag or Au) and [Ru₃H(CO)₉(µ₃-PPh){Ag(PPh₃)}] with PPh₃