The reaction of the dinuclear phosphinito bridged complex [(PHCy2)Pt(μ-PCy2){κ2P,O-μ-P(O)Cy2}Pt(PHCy2)](Pt-Pt) (1) with phenylacetylene affords the η1-alkenyl-μ,η1:η2-alkynyl complex [(η1-trans-(Ph)HCCH)(PHCy2)Pt(μ-PCy2)(μ,η1:η2-PhCC)Pt{κP-P(O)Cy2}(PHCy2)] (4) displaying a σ-bonded 2-phenylethenyl ligand and an alkynyl (μ-κCα:η2) bridge between the platinum atoms. Complex 4 was shown to form in two steps: initially, the attack of the first molecule of phenylacetylene gives the σ-acetylide complex [(PHCy2)(η1-PhCC)Pt1(μ-PCy2)Pt2(PHCy2){κP-P(OH)Cy2}](Pt-Pt) (5) featuring an intramolecular π-type hydrogen bond between the POH and the CC triple bond; fast reaction of 5 with a second molecule of phenylacetylene results in the oxidative addition of the terminal C-H bond of the second alkyne to Pt1 that, after rearrangements, leads to 4. When left in solution for two weeks, complex 4 spontaneously isomerizes completely to [(PHCy2)(η1-trans-(Ph)HCCH)Pt(μ-PCy2){κ2P,O-μ-P(O)Cy2}Pt(η1-PhCC)(PHCy2)] (7) displaying a 2-phenylethenyl ligand and a phenylethynyl group both σ-bonded to the metal. Density functional calculations at the B3LYP/LACV3P++∗∗//DFT/LACVP∗ level were carried out to study the thermodynamics of the formation of all considered complexes and to trace the mechanism of formation of the observed products.

Double addition of phenylacetylene onto the mixed bridge phosphinito-phosphanido Pt(i) complex [(PHCy2)Pt(μ-PCy2){κ2: P, O -μ-P(O)Cy2}Pt(PHCy2)](Pt-Pt)

Re N.;Marrone A.;Tolbatov I.;
2020-01-01

Abstract

The reaction of the dinuclear phosphinito bridged complex [(PHCy2)Pt(μ-PCy2){κ2P,O-μ-P(O)Cy2}Pt(PHCy2)](Pt-Pt) (1) with phenylacetylene affords the η1-alkenyl-μ,η1:η2-alkynyl complex [(η1-trans-(Ph)HCCH)(PHCy2)Pt(μ-PCy2)(μ,η1:η2-PhCC)Pt{κP-P(O)Cy2}(PHCy2)] (4) displaying a σ-bonded 2-phenylethenyl ligand and an alkynyl (μ-κCα:η2) bridge between the platinum atoms. Complex 4 was shown to form in two steps: initially, the attack of the first molecule of phenylacetylene gives the σ-acetylide complex [(PHCy2)(η1-PhCC)Pt1(μ-PCy2)Pt2(PHCy2){κP-P(OH)Cy2}](Pt-Pt) (5) featuring an intramolecular π-type hydrogen bond between the POH and the CC triple bond; fast reaction of 5 with a second molecule of phenylacetylene results in the oxidative addition of the terminal C-H bond of the second alkyne to Pt1 that, after rearrangements, leads to 4. When left in solution for two weeks, complex 4 spontaneously isomerizes completely to [(PHCy2)(η1-trans-(Ph)HCCH)Pt(μ-PCy2){κ2P,O-μ-P(O)Cy2}Pt(η1-PhCC)(PHCy2)] (7) displaying a 2-phenylethenyl ligand and a phenylethynyl group both σ-bonded to the metal. Density functional calculations at the B3LYP/LACV3P++∗∗//DFT/LACVP∗ level were carried out to study the thermodynamics of the formation of all considered complexes and to trace the mechanism of formation of the observed products.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11564/740585
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