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Mixed valence Pt(II),Pt(IV),Pt(II) complexes from a diplatinum(III) synthon and sulfur-based anions

AuthorsFortuño, Consuelo ; Martín, Antonio ; Mastrorilli, Piero; Todisco, Stefano; Latronico, Mario
Issue Date13-May-2019
PublisherAmerican Chemical Society
CitationOrganometallics 38(9): 2042-2052 (2019)
AbstractThe coordination of the S-based anions, thiophenoxide (PhS, a), ethyl xanthogenate (EtOCS, b), 2-mercaptopyridinate (pyS, c), and 2-mercaptopyrimidinate (pymS, d), to the central platinum atom of the trinuclear Pt(III),Pt(II) complex [(CF)Pt(μ-PPh)Pt(μ-PPh)Pt(CF)](Pt-Pt), 1, gives rise to three different types of complexes: (i) the Pt(II),Pt(II),Pt(II) complex [NBu][(CF)Pt(μ-PPh)Pt{κ-S,P-μ-(PhS)PPh}(μ-PPh)Pt(CF)], 2a; (ii) the Pt(II),Pt(IV),Pt(II) mixed valence complexes [NBu][(CF)Pt(μ-PPh)Pt(κ-S,S′-EtOCS)(μ-PPh)Pt(CF)], 3b, and [NBu][(CF)Pt(μ-PPh)Pt{κN,P-(pymS)PPh}(μ-PPh)Pt(CF)], 3d; and (iii) the Pt(II),Pt(II),Pt(II) derivatives [NBu][(CF)Pt(μ-PPh)Pt{κN,P-μ-(pyS)PPh}(μ-PPh)Pt(CF)], 4c, and [NBu][(CF)Pt(μ-PPh)Pt{κN,P-μ-(pymS)PPh}(μ-PPh)Pt(CF)], 4d. Complexes 2a, 4c, and 4d display new PhP(SL) ligands stemming from the reductive coupling of a PPh group and the S-based anions. Complex 2a exhibits a κ-S,P bridging coordination mode while 4c and 4d exhibit a κ-N,P mode in the solid state. In acetone solution, an equilibrium between the κ-N,P and the κ-S,P forms was ascertained for complexes with 2-mercaptopyrimidinate and 2-mercaptopyridinate by NMR techniques. Complex 4d evolved, in acetone solution at 323 K, to the Pt(II),Pt(II),Pt(II) complex [NBu][(CF)Pt(μ-PPh){κ-P,N-μ-(Pym)PPh}Pt(κ-S,P-μ-SPPh)(μ-PPh)Pt(CF)], 5d. The X-ray diffraction structures of the trinuclear complexes 3′b (the complex having the same anion as 3b but PhP=N=PPh as the countercation instead of NBu) and 4d are described.
Publisher version (URL)http://doi.org/10.1021/acs.organomet.9b00096
Identifiersdoi: 10.1021/acs.organomet.9b00096
e-issn: 1520-6041
issn: 0276-7333
Appears in Collections:(ISQCH) Artículos
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