Coordinatively unsaturated clusters: the rapid reversible addition of two carbonyl ligands to a trinuclear platinum cluster

Lloyd, Brian R.; Bradford, Arleen M.; Puddephatt, Richard J.

doi:10.1021/om00145a032

Cited by 24 publications

(7 citation statements)

References 3 publications

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“…This reflects the greater tendency for Ir to be coordinatively saturated. Under CO pressure, cluster 1 can also coordinate a second carbonyl ligand to form [Pt 3 (μ 3 -CO)(CO)(μ-dppm) 3 ] 2+ , 7 , which is isoelectronic and isostructural to 6 and exhibits similar spectroscopy and the same fluxional behavior as 6 .…”

Section: Resultsmentioning

confidence: 99%

Trinuclear and Tetranuclear Platinum−Iridium Cluster Complexes: A Remarkable Metal for Metal Substitution Reaction

et al. 1998

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The reaction of [Pt3(μ3-CO)(μ-dppm)3]2+, 1, dppm = Ph2PCH2PPh2, with [Ir(CO)4]- at low temperature gives [Pt3(μ3-CO)(μ-dppm)3{Ir(CO)4}]+, 2, and subsequent loss of CO leads to the butterfly complex [Pt3{Ir(CO)(μ-CO)2}(μ-CO)(μ-dppm)3]+, 3. Complex 3 reacts with L = P(OPh)3 to give [Pt3{IrL(μ-CO)2}(μ-CO)(μ-dppm)3]+, 4, which has been characterized by X-ray structure determination and has a butterfly structure with iridium at a wingtip position. Cluster 3 is thermally unstable and rearranges in solution to form the isomeric butterfly cluster cation [Pt2Ir{Pt(CO)(μ-CO)2}(CO)(μ-dppm)3]+, 5, in which the iridium atom now occupies a hinge position and whose formation involves phosphorus migration from platinum to iridium. Under CO, 5 eliminates one platinum atom to form the trimetallic complex [Pt2Ir(μ3-CO)(CO)(μ-dppm)3]+, 6. The overall reaction then involves displacement of a platinum atom from the 42-electron cluster cation 1 by {IrCO}- to give the 44-electron cation 6.

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Section: Resultsmentioning

confidence: 99%

Trinuclear and Tetranuclear Platinum−Iridium Cluster Complexes: A Remarkable Metal for Metal Substitution Reaction

et al. 1998

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“…Thus it has been shown in relation to the platinum complex by NMR involving different nuclei 185 that complex 59 can combine with a second CO molecule with formation of two isomers; the first with terminal and m 3 -coordinated carbonyls and the second with two m 3 -coordinated carbonyl ligands: Phosphines and phosphites (L) are coordinated as monodentate species in reactions with complex 59, forming [Pt 3 (m 3 -CO)(L)(m-dppm) 3 ] 2+ . The coordination of the carbonyl group and of the diphosphines does not then change.…”

Section: The Reactivity Of Clusters Containing the Metal In A Fractio...mentioning

confidence: 98%

Palladium carbonyl complexes

Stromnova¹,

Моисеев²

1998

Russ. Chem. Rev.

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“…12 In the only known triplatinum complexes with a carbonyl in the face position, stabilization by equatorial bidentate phosphine ligands is necessary and the carbonyl is actually fluxional between three-fold, two-fold, and terminal positions. 54,55 For ͓M 3 ͑CO͒ 3 ͑ϪCO͒ 3 ͔ 2Ϫ (MϭNi and Pt͒, calculations 33,56 indicate the highest-occupied molecular orbital ͑HOMO͒ is a delocalized symmetric combination of the six anti-bonding CO * orbitals. The next lower-energy MOs ͑HOMOs of the neutral͒ are derived from metal d orbitals.…”

Section: Structural Assignmentsmentioning

confidence: 99%

Binding energies of palladium carbonyl cluster anions: Collision-induced dissociation of Pd3(CO)n− (n=0–6)

Spasov

Ervin

1998

The Journal of Chemical Physics

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Articles you may be interested inStability of small Pd n ( n = 1 -7 ) clusters on the basis of structural and electronic properties: A density functional approach Measurement of the dissociation energies of anionic silver clusters ( Ag n − , n=2-11) by collision-induced dissociation J. Chem. Phys. 110, 5208 (1999); 10.1063/1.478416 Erratum: "Ligand and metal binding energies in platinum carbonyl cluster anions: Collision-induced dissociation of Pt m − and Pt m (CO) n " [J. Ligand and metal binding energies in platinum carbonyl cluster anions: Collision-induced dissociation of Pt m − and Pt m ( CO ) n − The bond dissociation energies of palladium trimer anion, Pd 3Ϫ , and its carbonyls, Pd 3 ͑CO͒ n Ϫ (n ϭ1 -6), are measured in the gas phase by the energy-resolved collision-induced dissociation method. The values obtained are D 0 (Pd 2 Ϫ ϪPd)ϭ2.26Ϯ0.36 eV for the bare cluster and D 0 (Pd 3 ͑CO͒ nϪ1Ϫ ϪCO)ϭ1.78Ϯ0.32 eV, 1.74Ϯ0.22 eV, 1.47Ϯ0.22 eV, 1.13Ϯ0.15 eV, 1.11 Ϯ0.15 eV, and 1.14Ϯ0.17 eV for nϭ1 -6, respectively, for the carbonyls. The results show a general decrease of the bond energy with an increasing number of carbonyls, with two relatively stable structures, Pd 3 ͑CO͒ 2 Ϫ and Pd 3 ͑CO͒ 6 Ϫ . A symmetric Pd 3 ͑CO͒ 2 Ϫ structure with two three-fold bridged carbonyls is postulated.

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Coordinatively unsaturated clusters: the rapid reversible addition of two carbonyl ligands to a trinuclear platinum cluster

Cited by 24 publications

References 3 publications

Trinuclear and Tetranuclear Platinum−Iridium Cluster Complexes: A Remarkable Metal for Metal Substitution Reaction

Trinuclear and Tetranuclear Platinum−Iridium Cluster Complexes: A Remarkable Metal for Metal Substitution Reaction

Palladium carbonyl complexes

Binding energies of palladium carbonyl cluster anions: Collision-induced dissociation of Pd3(CO)n− (n=0–6)

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