Title:
|
Structural preferences in phosphanylthiolato platinum(II) complexes
|
Author:
|
Duran i Carpintero, Josep; Polo Ortiz, Alfons; Real i Obradors, Juli; Benet-Buchholz, Jordi; Solà Puig, Miquel; Poater Teixidor, Albert
|
Abstract:
|
The transition-metal complexes of heterotopic phosphanylthiolato ligands are useful in various reactions which depend on the stereochemistry of the complexes. Bis-chelate complex [Pt(SCH₂CH₂PPh₂-κ²P,S₂)] (1) was obtained in good yields by direct base-free substitution reaction of the corresponding phosphanylthiol (HSCH₂CH₂PPh₂) with K₂PtCl₄ or by oxidative addition of the same phosphanylthiol to Pt(PPh₃)₄. In agreement with the antisymbiosis rule, complex 1 shows a cis -P,P arrangement in solid state crystallizing in the monoclinic system (C2 /c). Density functional theory (DFT) calculations on 1 reveal the right characteristics for the preferred cis -P,P arrangement, rationalizing its formation. Direct base-free reaction of [PtCl₂(1,5-cyclooctadiene)] with one equivalent of the same phosphanylthiol produce the trinuclear complex [PtCl(μ-SCH₂CH₂PPh₂-κ²P,S)]₃ (2) instead of the binuclear structure common in palladium and nickel derivatives. Crystals of 2 are triclinic (P ) showing a sulfur-bridging edge-sharing cyclic trinuclear complex with square-planar coordination geometry around the platinum atoms and a Pt₃S₃ cycle in skew-boat conformation. This preference for the trinuclear structure was rationalized mechanistically and through conceptual DFT. |
Subject(s):
|
-Bis-chelate complexes -Density functional calculations -P,S ligands -Platinum -Trinuclear complexes |
Rights:
|
open access
Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, sempre que no sigui amb finalitats comercials, i sempre que es reconegui l'autoria de l'obra original.
https://creativecommons.org/licenses/by-nc/3.0/ |
Document type:
|
Article |
Published by:
|
|
Share:
|
|
Uri:
|
https://ddd.uab.cat/record/185899
|