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Heteropolymetallic Architectures as Snapshots of Transmetallation Processes at Different Degrees of Transfer.


ABSTRACT: Novel heteropolymetallic architectures have been built by integrating Pd, Au and Ag systems. The dinuclear [(CNC)(PPh3 )Pd-G11 M(PPh3 )](ClO4 ) (G11 M=Au (3), Ag (4); CNC=2,6-diphenylpyridinate) and trinuclear [{(CNC)(PPh3 )Pd}2 G11 M](ClO4 ) (G11 M=Au (6), Ag (5)) complexes have been accessed or isolated. Structural and DFT characterization unveil striking interactions of one of the aryl groups of the CNC ligand(s) with the G11 M center, suggesting these complexes constitute models of transmetallation processes. Further analyses allow to qualitatively order the degree of transfer, proving that Au promotes the highest one and also that Pd systems favor higher degrees than Pt. Consistently, Energy Decomposition Analysis calculations show that the interaction energies follow the order Pd-Au > Pt-Au > Pd-Ag > Pt-Ag. All these results offer potentially useful ideas for the design of bimetallic catalytic systems.

SUBMITTER: Campillo D 

PROVIDER: S-EPMC9302616 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature

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Heteropolymetallic Architectures as Snapshots of Transmetallation Processes at Different Degrees of Transfer.

Campillo David D   Escudero Daniel D   Baya Miguel M   Martín Antonio A  

Chemistry (Weinheim an der Bergstrasse, Germany) 20220119 7


Novel heteropolymetallic architectures have been built by integrating Pd, Au and Ag systems. The dinuclear [(CNC)(PPh<sub>3</sub> )Pd-<sup>G11</sup> M(PPh<sub>3</sub> )](ClO<sub>4</sub> ) (<sup>G11</sup> M=Au (3), Ag (4); CNC=2,6-diphenylpyridinate) and trinuclear [{(CNC)(PPh<sub>3</sub> )Pd}<sub>2</sub> <sup>G11</sup> M](ClO<sub>4</sub> ) (<sup>G11</sup> M=Au (6), Ag (5)) complexes have been accessed or isolated. Structural and DFT characterization unveil striking interactions of one of the ary  ...[more]

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