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Issue 20, 2020
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Double addition of phenylacetylene onto the mixed bridge phosphinito–phosphanido Pt(i) complex [(PHCy2)Pt(μ-PCy2){κ2P,O-μ-P(O)Cy2}Pt(PHCy2)](Pt–Pt)

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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,η12-alkynyl complex [(η1-trans-(Ph)HC[double bond, length as m-dash]CH)(PHCy2)Pt(μ-PCy2)(μ,η12-PhC[triple bond, length as m-dash]C)Pt{κP-P(O)Cy2}(PHCy2)] (4) displaying a σ-bonded 2-phenylethenyl ligand and an alkynyl (μ-κCα2) 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-PhC[triple bond, length as m-dash]C)Pt1(μ-PCy2)Pt2(PHCy2){κP-P(OH)Cy2}](Pt–Pt) (5) featuring an intramolecular π-type hydrogen bond between the POH and the C[triple bond, length as m-dash]C 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)HC[double bond, length as m-dash]CH)Pt(μ-PCy2){κ2P,O-μ-P(O)Cy2}Pt(η1-PhC[triple bond, length as m-dash]C)(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.

Graphical abstract: Double addition of phenylacetylene onto the mixed bridge phosphinito–phosphanido Pt(i) complex [(PHCy2)Pt(μ-PCy2){κ2P,O-μ-P(O)Cy2}Pt(PHCy2)](Pt–Pt)

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Supplementary files

Article information


Submitted
11 Mar 2020
Accepted
29 Apr 2020
First published
06 May 2020

Dalton Trans., 2020,49, 6776-6789
Article type
Paper

Double addition of phenylacetylene onto the mixed bridge phosphinito–phosphanido Pt(I) complex [(PHCy2)Pt(μ-PCy2){κ2P,O-μ-P(O)Cy2}Pt(PHCy2)](Pt–Pt)

S. Todisco, M. Latronico, V. Gallo, N. Re, A. Marrone, I. Tolbatov and P. Mastrorilli, Dalton Trans., 2020, 49, 6776
DOI: 10.1039/D0DT00923G

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