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The reaction of the dinuclear phosphinito bridged complex [(PHCy2)Pt(μ-PCy2)κ2P,O-μ-P(O)Cy2Pt(PHCy2)](Pt-Pt) (1) with phenylacetylene affords the η1-alkenyl-μ,η1η2-alkynyl complex [(η1-trans-(Ph)HC[double bond, length as m-dash]CH)(PHCy2)Pt(μ-PCy2)(μ,η1η2-PhC[triple bond, length as m-dash]C)PtκP-P(O)Cy2(PHCy2)] (4) displaying a σ-bonded 2-phenylethenyl ligand and an alkynyl (μ-κCαη2) 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-acet
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