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Oxidatively induced P-O bond formation through reductive coupling between phosphido and acetylacetonate, 8-hydroxyquinolinate, and picolinate groups.
Inorg Chem. 2013 May 06; 52(9):5493-506.IC

Abstract

The dinuclear anionic complexes [NBu4][(RF)2M(II)(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)2M(II)(μ-I)(μ-PPh2)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-OC6H4NO (Ph2P-pic). In these cases, the isolated derivatives [NBu4][(Ph2P-pic)(RF)Pt(II)(μ-I)(μ-PPh2)M(II)(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)2Pt(II)(μ-PPh2)2Pt(II)(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)2Pt(II)(μ-I)(μ-PPh2)Pt(II)(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.

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Authors+Show Affiliations

Arias A
Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea, Universidad de Zaragoza-C.S.I.C., E-50009 Zaragoza, Spain.
Forniés J
No affiliation info available
Fortuño C
No affiliation info available
Martín A
No affiliation info available
Mastrorilli P
No affiliation info available
Todisco S
No affiliation info available
Latronico M
No affiliation info available
Gallo V
No affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

23596965

Citation

Arias, Andersson, et al. "Oxidatively Induced P-O Bond Formation Through Reductive Coupling Between Phosphido and Acetylacetonate, 8-hydroxyquinolinate, and Picolinate Groups." Inorganic Chemistry, vol. 52, no. 9, 2013, pp. 5493-506.
Arias A, Forniés J, Fortuño C, et al. Oxidatively induced P-O bond formation through reductive coupling between phosphido and acetylacetonate, 8-hydroxyquinolinate, and picolinate groups. Inorg Chem. 2013;52(9):5493-506.
Arias, A., Forniés, J., Fortuño, C., Martín, A., Mastrorilli, P., Todisco, S., Latronico, M., & Gallo, V. (2013). Oxidatively induced P-O bond formation through reductive coupling between phosphido and acetylacetonate, 8-hydroxyquinolinate, and picolinate groups. Inorganic Chemistry, 52(9), 5493-506. https://doi.org/10.1021/ic4004005
Arias A, et al. Oxidatively Induced P-O Bond Formation Through Reductive Coupling Between Phosphido and Acetylacetonate, 8-hydroxyquinolinate, and Picolinate Groups. Inorg Chem. 2013 May 6;52(9):5493-506. PubMed PMID: 23596965.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Oxidatively induced P-O bond formation through reductive coupling between phosphido and acetylacetonate, 8-hydroxyquinolinate, and picolinate groups. AU - Arias,Andersson, AU - Forniés,Juan, AU - Fortuño,Consuelo, AU - Martín,Antonio, AU - Mastrorilli,Piero, AU - Todisco,Stefano, AU - Latronico,Mario, AU - Gallo,Vito, Y1 - 2013/04/18/ PY - 2013/4/20/entrez PY - 2013/4/20/pubmed PY - 2013/4/20/medline SP - 5493 EP - 506 JF - Inorganic chemistry JO - Inorg Chem VL - 52 IS - 9 N2 - The dinuclear anionic complexes [NBu4][(RF)2M(II)(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)2M(II)(μ-I)(μ-PPh2)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-OC6H4NO (Ph2P-pic). In these cases, the isolated derivatives [NBu4][(Ph2P-pic)(RF)Pt(II)(μ-I)(μ-PPh2)M(II)(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)2Pt(II)(μ-PPh2)2Pt(II)(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)2Pt(II)(μ-I)(μ-PPh2)Pt(II)(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. SN - 1520-510X UR - https://www.unboundmedicine.com/medline/citation/23596965/Oxidatively_induced_P_O_bond_formation_through_reductive_coupling_between_phosphido_and_acetylacetonate_8_hydroxyquinolinate_and_picolinate_groups_ L2 - https://doi.org/10.1021/ic4004005 DB - PRIME DP - Unbound Medicine ER -