Palladium iminophosphorane complexes: the pre-cursors to the missing link in triphenylphosphane chalcogenide metallacycles

Fernández-Figueiras, Adolfo; Lucio‐Martínez, Fátima; Munín‐Cruz, Paula; Polo-Ces, Paula; Reigosa, Francisco; Adams, Harry; Pereira, Mariana; Vila, José M.

doi:10.1039/c8dt03062f

Cited by 10 publications

(6 citation statements)

References 45 publications

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“…As for the other phosphine chalcogenide derivatives, a literature survey has revealed only a few examples of Pd(II) and Pt(II) pincer complexes with the coordinated phosphoryl group (Figure ). Nevertheless, this result was expected given the hard donor nature of the oxygen atom . Complexes I and II were smoothly synthesized by direct cyclopalladation of the corresponding functionalized amide or ketone.…”

Section: Introductionmentioning

confidence: 99%

Extending the Application Scope of Organophosphorus(V) Compounds in Palladium(II) Pincer Chemistry

et al. 2019

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1-Dimethylthiocarbamoyloxy-3-diphenylphosphinobenzene was used as a key precursor for the synthesis of a whole series of organophosphorus(V) pincer ligands combining thiocarbamate donor group with PX coordination arm, where X = S, Se, O, NR (R = Ph, 4-NO 2 C 6 H 4 , COO t Bu, CH 2 Ph) or CHR′ (R′ = COOEt, CN). Direct cyclopalladation of the ligands obtained (used either as individual compounds or generated in situ in the reaction mixture) afforded hybrid pincer complexes with fiveand sixmembered fused metallacycles. In the case of phosphine sulfide and phosphine selenide derivatives, the cyclopalladation can readily be accomplished in CH 2 Cl 2 at room temperature, leading to the target pincer complexes in high yields. Their phosphine imide and phosphonium ylide counterparts can also be obtained under mild reaction conditions, but the yields strongly depend on the ligand stability (35−93%). Even in the case of the phosphoryl-functionalized ligand, the desired pincer-type complex was synthesized in ca. 15% yield, although the main direction of metalation was C(sp 3 )−H bond activation of one of the methyl groups in OC(S)NMe 2 moiety. Realization of κ 3 -S,C,X-coordination (X = S, Se, O, N, or C) in the resulting pincer complexes was unambiguously confirmed based on the multinuclear NMR ( 1 H, 13 C, 31 P, and 77 Se) and IR spectroscopic data. Comparative single-crystal XRD analyses allowed for outlining the main structural features of the palladacycles obtained depending on the nature of ancillary P(V)-donor group. In addition, the possibility of solid-phase cyclopalladation was demonstrated by the examples of phosphine chalcogenide and stable phosphine imide ligands. In most cases, this approach afforded the desired complexes with the same or even higher efficiencies than the conventional solution-based method. Preliminary investigations on the cytotoxic activity of some of the complexes obtained against several human cancer cell lines revealed the high activity of phosphine imide-based palladacycles, rendering further studies in this field promising.

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Section: Introductionmentioning

confidence: 99%

Extending the Application Scope of Organophosphorus(V) Compounds in Palladium(II) Pincer Chemistry

et al. 2019

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“…In Scheme 1 , some relevant examples of iminophosphorane palladacycles are depicted which show the terdentate [C,N,S] aniline complex by Grévy [ 31 ] I, the [C,N,S] [ 21 ] and [C,N] [ 16 ] structures II and III by Urriolabeitia, and the terdentate [C,N,O] [ 32 ] IV and tetradentate [C,N:C,N] [ 33 ] V dinuclear complexes by Vila. In all cases, the corresponding iminophosphorane was prepared from the azide by using a PR 3 ligand, where appropriate, in the ensuing palladacycles, with a bridging diphosphine; the latter holds together the two palladium iminophosphorane moieties.…”

Section: Introductionmentioning

confidence: 99%

Cyclometallated Palladium(II) Complexes: An Approach to the First Dinuclear Bis(iminophosphorane)phosphane-[C,N,S] Metallacycle

et al. 2022

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Treatment of bis(iminophosphorane)phosphane ligands 2a–2e with Li2PdCl4 gave a set of novel diphosphane-derived complexes bearing two metallacycle rings, each one enclosing a P=N double bond: the unprecedented bis(iminophosphorane)phosphane-[C,N,S] palladacycles. In the case of the ligand derived from bis(diphenylphosphino)methane, 2a, both the single and the double palladacycle complexes were obtained. Reaction of 3a with bis(diphenylphosphino)ethane did not yield the expected product with the diphosphane bonded to both palladium atoms, but rather the novel coordination compound 5. The crystal structures of 3c and 5 are described.

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“…Among all these metals, palladium is one of the most interesting. Its coordinative ability to many donor atoms [3][4][5], including carbon atoms to synthesized cyclometallated compounds [6][7][8], makes this metal an excellent choice. The square-planar geometry facilitates the coordination of multidentate ligands [9,10], creating very stable complexes.…”

Section: Introductionmentioning

confidence: 99%

Palladium Cyclometallated Compounds: Evaluation of Their Catalytic Activity in Cross-Coupling Reactions

Rúa‐Sueiro

Munín‐Cruz

Bermúdez-Fernández

et al. 2022

The 2nd International Electronic Conference on Catalysis Sciences—A Celebration of Catalysts 10th Anniversary

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Palladium iminophosphorane complexes: the pre-cursors to the missing link in triphenylphosphane chalcogenide metallacycles

Abstract: A dinuclear iminophosphorane palladacycle produces the missing link in the triphenylphosphane chalcogenide series of metallacycles.

Cited by 10 publications

References 45 publications

Extending the Application Scope of Organophosphorus(V) Compounds in Palladium(II) Pincer Chemistry

Extending the Application Scope of Organophosphorus(V) Compounds in Palladium(II) Pincer Chemistry

Cyclometallated Palladium(II) Complexes: An Approach to the First Dinuclear Bis(iminophosphorane)phosphane-[C,N,S] Metallacycle

Palladium Cyclometallated Compounds: Evaluation of Their Catalytic Activity in Cross-Coupling Reactions

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