Uptake of one and two molecules of 1,3-butadiene by platinum bis(dithiolene): A theoretical study

Li Dang, Shao Fei Ni, Michael B. Hall, Edward Brothers

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Abstract

Platinum bis(dithiolene) complexes have reactivity toward alkenes like nickel bis(dithiolene) complexes. We examined the uptake of 1,3-butadiene by platinum bis(dithiolene) [Pt(tfd)2] (tfd = S2C2(CF3)2) via a density functional theory study; both 1,2- and 1,4-additions of 1,3-butadiene to the ligands of Pt(tfd)2 to form both interligand and intraligand adducts were studied. For single 1,3-butadiene addition, direct 1,4-addition on interligand S-S, 1,2- addition on intraligand S-S, and 1,4-addition on intraligand S-C are all feasible at room temperature and are controlled by the symmetry of the highest occupied molecular orbital of 1,3- butadiene and the lowest unoccupied molecular orbital of Pt(tfd)2. However, the formation of the interligand S-S adduct through 1,4- addition of one molecule of cis-1,3-butadiene is the most favorable route, with a reaction barrier of 9.3 kcal/mol. The other two addition processes cannot compete with this one due to both higher reaction barriers and unstable adducts. Other possible pathways, such as formation of cis-interligand S-S adduct from 1,2- addition of one molecule of 1,3-butadiene via a twisted trans-interligand S-S adduct, have higher barriers. Our calculated results show that 1,4-addition of a single molecule of 1,3-butadiene on the interligand S-S gives the kinetically stable product by a onestep pathway. But of at least equal importance is the apofacial 1,4-addition of two molecules of 1,3-butadiene on the intraligand S-C of the same ligand on Pt(tfd)2, which yields the thermodynamically stable product, obtained via a short lifetime intermediate, the 1:1 intraligand S-C adduct, being formed through several pathways. The calculated results in this study well explain the experimental observation that 1:1 interligand S-S adduct was formed in a short time, and the intraligand S-C adduct from two molecules of cis-1,3-butadiene was accumulated in 20 h at 50° and characterized by X-ray crystallography.

Original languageEnglish
Pages (from-to)9692-9702
Number of pages11
JournalInorganic Chemistry
Volume53
Issue number18
DOIs
Publication statusPublished - 15 Sep 2014

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butadiene
Platinum
platinum
Theoretical Models
adducts
Molecules
molecules
Molecular orbitals
molecular orbitals
Ligands
1,3-butadiene
X ray crystallography
X Ray Crystallography
ligands
Alkenes
Nickel
products
Density functional theory
alkenes
crystallography

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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Uptake of one and two molecules of 1,3-butadiene by platinum bis(dithiolene) : A theoretical study. / Dang, Li; Ni, Shao Fei; Hall, Michael B.; Brothers, Edward.

In: Inorganic Chemistry, Vol. 53, No. 18, 15.09.2014, p. 9692-9702.

Research output: Contribution to journalArticle

Dang, Li ; Ni, Shao Fei ; Hall, Michael B. ; Brothers, Edward. / Uptake of one and two molecules of 1,3-butadiene by platinum bis(dithiolene) : A theoretical study. In: Inorganic Chemistry. 2014 ; Vol. 53, No. 18. pp. 9692-9702.
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abstract = "Platinum bis(dithiolene) complexes have reactivity toward alkenes like nickel bis(dithiolene) complexes. We examined the uptake of 1,3-butadiene by platinum bis(dithiolene) [Pt(tfd)2] (tfd = S2C2(CF3)2) via a density functional theory study; both 1,2- and 1,4-additions of 1,3-butadiene to the ligands of Pt(tfd)2 to form both interligand and intraligand adducts were studied. For single 1,3-butadiene addition, direct 1,4-addition on interligand S-S, 1,2- addition on intraligand S-S, and 1,4-addition on intraligand S-C are all feasible at room temperature and are controlled by the symmetry of the highest occupied molecular orbital of 1,3- butadiene and the lowest unoccupied molecular orbital of Pt(tfd)2. However, the formation of the interligand S-S adduct through 1,4- addition of one molecule of cis-1,3-butadiene is the most favorable route, with a reaction barrier of 9.3 kcal/mol. The other two addition processes cannot compete with this one due to both higher reaction barriers and unstable adducts. Other possible pathways, such as formation of cis-interligand S-S adduct from 1,2- addition of one molecule of 1,3-butadiene via a twisted trans-interligand S-S adduct, have higher barriers. Our calculated results show that 1,4-addition of a single molecule of 1,3-butadiene on the interligand S-S gives the kinetically stable product by a onestep pathway. But of at least equal importance is the apofacial 1,4-addition of two molecules of 1,3-butadiene on the intraligand S-C of the same ligand on Pt(tfd)2, which yields the thermodynamically stable product, obtained via a short lifetime intermediate, the 1:1 intraligand S-C adduct, being formed through several pathways. The calculated results in this study well explain the experimental observation that 1:1 interligand S-S adduct was formed in a short time, and the intraligand S-C adduct from two molecules of cis-1,3-butadiene was accumulated in 20 h at 50° and characterized by X-ray crystallography.",
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AU - Brothers, Edward

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