New [Pt3(.mu.3-CO)(.mu.-Ph2PCH2PPh2)3L]2+ clusters, L = phosphine or phosphite ligand, containing an asymmetric Pt3(.mu.3-CO) group and the crystal structure of the complex with L = P(OPh)3

Bradford, Arleen M.; Douglas, Graeme; Manojlović-Muir, Ljubica; Muir, Kenneth W.; Puddephatt, Richard J.

doi:10.1021/om00116a017

Cited by 45 publications

(26 citation statements)

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“…Note that the diphosphine ligands adopt a chelating mode in cluster 3, whereas the many crystallographically characterized Pd 3 (LL) 3 and Pt 3 (LL) 3 systems with LL ) dppm display a bridging mode for the smaller bite diphosphinomethane ligand. [52][53][54][55][57][58][59][60][61][62][63][64] In the structure of the somewhat related [Pt 3 (dppe) 3 (H) 3 ] + , the diphosphine also adopts a chelating mode. 65 As mentioned above, a Pt complex having the same stoichiometry, [Pt 3 (dppe) 3 (H) 2 ] 2+ , has previously been reported but not structurally characterized.…”

Section: Crystallographic Analysesmentioning

confidence: 99%

Pd(I) Phosphine Carbonyl and Hydride Complexes Implicated in the Palladium-Catalyzed Oxo Process

et al. 2008

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Reduction of compound "Pd(bcope)(OTf)2" [bcope = (c-C8H14-1,5)PCH2CH2P(c-C8H14-1,5); OTf = O3SCF3] with H2/CO yields a mixture of Pd(I) compounds [Pd2(bcope)2(CO)2](OTf)2 (1) and [Pd2(bcope)2(mu-CO)(mu-H)](OTf) (2), whereas reduction with H2 or Ph3SiH in the absence of CO leads to [Pd3(bcope)3(mu3-H)2](OTf)2 (3). Exposure of 3 to CO leads to 1 and 2. The structures of 1 and 3 have been determined by X-ray diffraction. Complex [Pd2(bcope)2(CO)2](2+) displays a metal-metal bonded structure with a square planar environment for the Pd atoms and terminally bonded CO ligands and is fluxional in solution. DFT calculations aid the interpretation of this fluxional behavior as resulting from an intramolecular exchange of the two inequivalent P atom positions via a symmetric bis-CO-bridged intermediate. A cyclic voltammetric investigation reveals a very complex redox behavior for the "Pd(bcope)(OTf)2"/CO system and suggests possible pathways leading to the formation of the various observed products, as well as their relationship with the active species of the PdL2(2+)/CO/H2-catalyzed oxo processes (L2 = diphosphine ligands).

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Section: Crystallographic Analysesmentioning

confidence: 99%

Pd(I) Phosphine Carbonyl and Hydride Complexes Implicated in the Palladium-Catalyzed Oxo Process

et al. 2008

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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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“…NO and CO adsorption on well‐defined single‐crystal surfaces has been studied using various experimental techniques including infrared reflection‐adsorption (IRAS) and electron energy loss (EELS) spectroscopies, temperature‐programmed desorption (TPD) and low‐energy molecular beam scattering (LEMS) 4–6. IRAS has also been used for the investigation of carbonyl and nitrosyl complexes of Pd and Pt isolated in rare‐gas matrices,7, 8 whereas clusters have been investigated mostly within the framework of organometallic chemistry 9–13. However, the interpretation of the experiments is often far from straightforward and reliable conclusions may be obtained only from detailed comparison of experimental and theoretical data.…”

Section: Introductionmentioning

confidence: 99%

Interaction of NO molecules with Pd clusters: Ab initio density–functional study

2009

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The adsorption of NO molecules on small Pd(n) (n = 1-6) clusters has been studied using first-principles density-functional theory. Three adsorption sites were considered: vertex (on-top), bridge, and hollow. Adsorption is strong, ranging from 2 to 3 eV. In all cases NO adsorbs in a bent configuration. Calculated shifts in N-O bond vibration frequencies (with anharmonic corrections) agree very well with available experimental data. In contrast to metallic Pd surfaces, adsorption of NO on palladium clusters causes considerable changes in geometry around adsorption site because palladium d-orbitals rehybridize to maximize the overlap with NO orbitals (mainly the antibonding pi*). Thus, the overall energetic effect of NO adsorption is the result of two competing processes: lowering of the total energy through tighter bonding with NO and rising the energy due to cluster deformation. The Pd(n)-NO bond creation is governed by electron transfer from Pd-d orbitals into the NO pi*. As a result, the Pd cluster becomes locally demagnetized (with total magnetic moment of 1 micro(B) located at Pd atoms not connected to NO) and the NO molecule is activated: the N-O bond length is increased and the vibration frequency is redshifted.

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New [Pt3(.mu.3-CO)(.mu.-Ph2PCH2PPh2)3L]2+ clusters, L = phosphine or phosphite ligand, containing an asymmetric Pt3(.mu.3-CO) group and the crystal structure of the complex with L = P(OPh)3

Cited by 45 publications

References 0 publications

Pd(I) Phosphine Carbonyl and Hydride Complexes Implicated in the Palladium-Catalyzed Oxo Process

Pd(I) Phosphine Carbonyl and Hydride Complexes Implicated in the Palladium-Catalyzed Oxo Process

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

Interaction of NO molecules with Pd clusters: Ab initio density–functional study

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