Theoretical study of the protonation of [Pt3(μ-L)3(L′)3] (L=CO, SO2, CNH; L′=PH3, CNH)

Mendizábal, Fernando; Donoso, Daniela; Burgos, Darwin

doi:10.1016/j.cplett.2011.08.068

Cited by 11 publications

(7 citation statements)

References 30 publications

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“…Indeed, trinuclear clusters of M(0), such as [Pt 3 (CO) 3 (P(C 6 H 11 ) 3 ) 4 ], [M 3 (CO) 3 L 3 ] (M = Pd, L = P( t -Bu) 3 , PPh( t -Bu) 2 ; M = Pt, L = PPh( t -Bu) 2 ), [Pt 3 (SO 2 ) 3 (PPh 3 ) 3 ], and [Pt 3 (CN- t -Bu) 6 ] were characterized and investigated a long time ago. [Pt 3 (PPh 3 ) 2 (PPh 2 ) 3 (Ph)] with two short Pt–Pt bonds (2.79 Å) and the nonbonding Pt–Pt of 3.63 Å was synthesized from [Pt(PPh 3 ) 4 ] and reported to have a mixed oxidation states with two Pt(I) and one Pt(II). , Palladium cluster [Pd 3 Cl(PPh 2 ) 2 (PPh 3 ) 3 ][BF 4 ] with Pd in an oxidation state other than zero was also well-characterized by Dixon and co-workers. , Additionally, previous works have shown that M 3 can act as either Lewis base or Lewis acid, which enables the formation of the “open face” (or half-sandwich) or the “full face” (or sandwich) structure by interacting with H + , MPH 3 + , Tl + , and Cd 2+ ions. ,− …”

Section: Introductionmentioning

confidence: 99%

Manipulating Stabilities and Catalytic Properties of Trinuclear Metal Clusters through Tuning the Chemical Bonding: H₂ Adsorption and Activation

Xing

Xiao

et al. 2017

J. Phys. Chem. C

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Chemical bonding involving metal−metal (M−M) and metal−ligand (M−L) interactions provides an opportunity to tune the stabilities and catalytic properties of metal clusters. We report here the electronic and bonding properties of a series of trinuclear clusters [M 3 X 3 (PR 3 ) 3 ] + (M = Ni, Pd, Pt; X = F, Cl, Br, I; R = H) to explore the electronic effect on the adsorption and activation of H 2 and other small molecules. The chemical bonding model of M 3 is discussed in detail, and the formal +4/3 oxidation state of the metal element in the M 3 cluster is proposed. Metallic σ-aromaticity is also found in the trinuclear clusters. We have shown that the stability and the catalytic activity of the trinuclear clusters can be tuned by altering the energies and compositions of M−M and M−L chemical bonding orbitals. The performance of H 2 dissociative adsorption on these clusters can be explained by the orbital interactions. Relativistic effects also play a significant role in determining the activity of H 2 adsorption. This finding provides an example for controlling catalytic properties through tuning chemical bonding of metal clusters.

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Section: Introductionmentioning

confidence: 99%

Manipulating Stabilities and Catalytic Properties of Trinuclear Metal Clusters through Tuning the Chemical Bonding: H₂ Adsorption and Activation

Xing

Xiao

et al. 2017

J. Phys. Chem. C

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“…The electronic chemical potential and hardness are computed from ionization energy and electron affinity, with those at the ab initio level (HF and MP2) better than those at the DFT level (B3LYP and PBE). It is known that in calculations with DFT the electron density decays faster than at the ab initio level [33]. This is manifested in the µ and η values in Table 8.…”

Section: Reactivity Of Electrophilic Clustersmentioning

confidence: 95%

“…Moreover, a local electrophilicity has been introduced to analyze the electrophile-nucleophile reactions. It is defined as An analysis of electrophilicity on platinum atom (ω Pt -) provides the local information in a molecule being attacked by an electrophile fragment [33] .…”

Section: Models and Computational Methodsmentioning

confidence: 99%

THEORETICAL STUDY OF COMPLEXES OF THE TYPE [Pt3(M-L)3(L')3J-X (L=CO,SO2,CNH; L'=PH3,CNH; X=Tl+, Hg0, MPH3+ (M = Cu, Au, Ag))

Mendizábal

Donoso

Salatar

2013

J. Chil. Chem. Soc.

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The interaction between the [Pt 3 (μ-L) 3 (L`) 3 ] cluster (L = CO, SO 2 , CNH; L` = PH 3 , CNH) and a series of fragments X (Tl + , Hg(0), AuPH 3 + , CuPH 3 + and AgPH 3 +) was studied using ab initio methodology. The calculations suggest that the complexes formed are stable. We have studied these complexes at the HF, MP2, B3LYP and PBE levels of theory. The magnitude of the interaction energies and Pt 3-MPH 3 + distances indicate a substantial covalent character of the bond. On the other hand, in [Pt 3 (μ-L) 3 (L`) 3 ]-X (Tl + and Hg) the energy magnitudes are in the order of metallophilic interaction, which indicates that the dispersion and ionic terms are found as the main contribution to stability. These results have been confirmed by orbital diagrams. In addition, the Fukui index of electrophilic attack and electrophilicity index on the [Pt 3 (μ-L) 3 (L`) 3 ] clusters were used to explore possible sites that may play a role in chemical reactivity.

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“…Mendizabal and coworkers studied the noncovalent interaction between several d 10 ‐d 10 macrocycles and arene fragments, denoting the nature of their formation …”

Section: Theoretical Backgroundmentioning

confidence: 99%

Advances in bonding and properties of inorganic systems from relativistic calculations in Latin America

MacLeod‐Carey

Caramori

Guajardo‐Maturana

et al. 2018

Int J of Quantum Chemistry

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The inclusion of relativistic effects to understand chemical structures and related properties brings to the scientific community challenging study cases, showing the rich diversity of chemical behavior of the different elements along the periodic table. The results highlighted here represent applications of relativistic methodologies to study the nature of bonding and a prediction of optical and magnetic properties of meaningful chemical entities containing heavy atoms, all made in Latin America. The good agreement between calculated and experimental observables in many molecular and cluster‐like systems ratifies that relativistic methods are appropriate to describe these entities realistically. We expect to enhance our knowledge in these methodologies, currently included in doctoral programs in our region.

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Theoretical study of the protonation of [Pt3(μ-L)3(L′)3] (L=CO, SO2, CNH; L′=PH3, CNH)

Cited by 11 publications

References 30 publications

Manipulating Stabilities and Catalytic Properties of Trinuclear Metal Clusters through Tuning the Chemical Bonding: H₂ Adsorption and Activation

Manipulating Stabilities and Catalytic Properties of Trinuclear Metal Clusters through Tuning the Chemical Bonding: H₂ Adsorption and Activation

THEORETICAL STUDY OF COMPLEXES OF THE TYPE [Pt3(M-L)3(L')3J-X (L=CO,SO2,CNH; L'=PH3,CNH; X=Tl+, Hg0, MPH3+ (M = Cu, Au, Ag))

Advances in bonding and properties of inorganic systems from relativistic calculations in Latin America

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Theoretical study of the protonation of [Pt3(μ-L)3(L′)3] (L=CO, SO2, CNH; L′=PH3, CNH)

Cited by 11 publications

References 30 publications

Manipulating Stabilities and Catalytic Properties of Trinuclear Metal Clusters through Tuning the Chemical Bonding: H2 Adsorption and Activation

Manipulating Stabilities and Catalytic Properties of Trinuclear Metal Clusters through Tuning the Chemical Bonding: H2 Adsorption and Activation

THEORETICAL STUDY OF COMPLEXES OF THE TYPE [Pt3(M-L)3(L')3J-X (L=CO,SO2,CNH; L'=PH3,CNH; X=Tl+, Hg0, MPH3+ (M = Cu, Au, Ag))

Advances in bonding and properties of inorganic systems from relativistic calculations in Latin America

Contact Info

Product

Resources

About

Manipulating Stabilities and Catalytic Properties of Trinuclear Metal Clusters through Tuning the Chemical Bonding: H₂ Adsorption and Activation

Manipulating Stabilities and Catalytic Properties of Trinuclear Metal Clusters through Tuning the Chemical Bonding: H₂ Adsorption and Activation