Electronic underpinnings of phosphido-bridged Pt-3 clusters and the questioned stereochemistry of a uniquely reported 46e(-) species (Articolo in rivista)

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  • Electronic underpinnings of phosphido-bridged Pt-3 clusters and the questioned stereochemistry of a uniquely reported 46e(-) species (Articolo in rivista) (literal)
Anno
  • 2015-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1016/j.ica.2014.09.040 (literal)
Alternative label
  • Manca, Gabriele; Ienco, Andrea; Messaoudi, Abdelatif; Mealli, Carlo (2015)
    Electronic underpinnings of phosphido-bridged Pt-3 clusters and the questioned stereochemistry of a uniquely reported 46e(-) species
    in Inorganica Chimica Acta (Testo stamp.)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Manca, Gabriele; Ienco, Andrea; Messaoudi, Abdelatif; Mealli, Carlo (literal)
Pagina inizio
  • 322 (literal)
Pagina fine
  • 328 (literal)
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  • 424 (literal)
Rivista
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  • 7 (literal)
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • Consiglio Nazionale delle Ricerche (CNR); University of Batna (literal)
Titolo
  • Electronic underpinnings of phosphido-bridged Pt-3 clusters and the questioned stereochemistry of a uniquely reported 46e(-) species (literal)
Abstract
  • The compound H(PEt3)(3)Pt-3(mu-PPh2)(3) is the unique example of a 46e(-) phosphido-bridged triangular cluster, but its X-ray assigned stereochemistry appears questionable. In particular, the H-free P3Pt3(mu-P)(3) metal core is identical to that of the 46e(-) cation [(PEt3)(3)Pt-3(mu-PPh2)(3)](+) in two salts of the same publication. Also, the lack of a distortional effect due to the upright and strongly-bound hydride ligand is suspicious and intriguing aspects emerge from the inconsistent electronic structure. Although H(PEt3)(3)Pt-3(mu-PPh2)(3) is fully validated by IR and NMR spectra, DFT optimizations never reproduced the reported structure but highlighted a different stereochemistry not in contrast with the spectroscopic response. Here, a formal Pt(II) ion is almost separated with an essential square-planar coordination, completed by two trans-axial ligands (H and Et3P) perpendicular to the Pt-3 plane. Provided the chemical reliability of the in silico molecule, the crystals of the experimental structure have likely contents other than the hydridic cluster and the co-crystallized Ph2PH molecule. As a working hypothesis, the Pt-H and P-H linkages of the distinct components may have reacted together with H-2 release, and subsequent crstallization of the salt [(PEt3)(3)Pt-3(mu-PPh2)(3)](+)/[Ph2P]. This would explain the equal geometries of the putative 46e(-) cluster and the H-free 46e(-) cation. In the lack of any experimental X-ray dataset, the proposed crystal formulation could not be fully validated, but various aspects support its reliability. Essentially, the problem may arise from the misplacement of two H atoms (those of the mentioned Pt-H and P-H linkages), which does not affect the structural refinement but determines the chemical inconsistency. (C) 2014 Elsevier B.V. All rights reserved. (literal)
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