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Oxidatively induced P-O bond formation through reductive coupling between phosphido and acetylacetonate, 8-hydroxyquinolinate, and picolinate groups

AuthorsArias, Andersson ; Forniés, Juan ; Fortuño, Consuelo ; Martín, Antonio ; Mastrorilli, Piero; Todisco, Stefano; Latronico, Mario; Gallo, Vito
Issue Date2013
PublisherAmerican Chemical Society
CitationInorganic Chemistry 52(9): 5493-5506 (2013)
AbstractThe dinuclear anionic complexes [NBu4][(RF) 2MII(μ-PPh2)2M′ II(N∥O)] (RF = C6F5. N∥O = 8-hydroxyquinolinate, hq; M = M′ = Pt 1; Pd 2; M = Pt, M′ = Pd, 3. N∥O = o-picolinate, pic; M = Pt, M′ = Pt, 4; Pd, 5) are synthesized from the tetranuclear [NBu4] 2[{(RF)2Pt(μ-PPh2) 2M(μ-Cl)}2] by the elimination of the bridging Cl as AgCl in acetone, and coordination of the corresponding N,O-donor ligand (1, 4, and 5) or connecting the fragments >cis-[(RF) 2M(μ-PPh2)2]2-> and >M′(N∥O)> (2 and 3). The electrochemical oxidation of the anionic complexes 1-5 occurring under HRMS(+) conditions gave the cations [(RF)2M(μ-PPh2) 2M′(N∥O)]+, presumably endowed with a M(III),M′(III) core. The oxidative addition of I2 to the 8-hydroxyquinolinate complexes 1-3 triggers a reductive coupling between a PPh2 bridging ligand and the N,O-donor chelate ligand with formation of a P-O bond and ends up in complexes of platinum(II) or palladium(II) of formula [(RF)2MII(μ-I)(μ-PPh 2)M′II(P,N-PPh2hq)], M = M′ = Pt 7, Pd 8; M = Pt, M′ = Pd, 9. Complexes 7-9 show a new Ph2P- OC9H6N (Ph2P-hq) ligand bonded to the metal center in a P,N-chelate mode. Analogously, the addition of I2 to solutions of the o-picolinate complexes 4 and 5 causes the reductive coupling between a PPh2 bridging ligand and the starting N,O-donor chelate ligand with formation of a P-O bond, forming Ph2P-OC 6H4NO (Ph2P-pic). In these cases, the isolated derivatives [NBu4][(Ph2P-pic)(RF)Pt II(μ-I)(μ-PPh2)MII(RF)I] (M = Pt 10, Pd 11) are anionic, as a consequence of the coordination of the resulting new phosphane ligand (Ph2P-pic) as monodentate P-donor, and a terminal iodo group to the M atom. The oxidative addition of I2 to [NBu4][(RF)2PtII(μ-PPh 2)2PtII(acac)] (6) (acac = acetylacetonate) also results in a reductive coupling between the diphenylphosphanido and the acetylacetonate ligand with formation of a P-O bond and synthesis of the complex [NBu4][(RF)2PtII(μ-I)(μ- PPh2)PtII(Ph2P-acac)I] (12). The transformations of the starting complexes into the products containing the P-O ligands passes through mixed valence M(II),M′(IV) intermediates which were detected, for M = M′ = Pt, by spectroscopic and spectrometric measurements. © 2013 American Chemical Society.
Identifiersdoi: 10.1021/ic4004005
issn: 0020-1669
e-issn: 1520-510X
Appears in Collections:(ISQCH) Artículos
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