Lower- and upper-rim-modified derivatives of 1,3,5-triaza-7-phosphaadamantane: Coordination chemistry and applications in catalytic reactions in water

Gonsalvi, Luca; Guerriero, Antonella; Hapiot, F.; Krogstad, Donald A.; Monflier, Éric; Reginato, Gianna; Peruzzini, Maurizio

doi:10.1351/pac-con-12-07-10

Cited by 24 publications

(11 citation statements)

References 26 publications

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“…The water-solubility of 1,3,5-triaza-7-phosphaadamantane (PTA), its diverse mode of coordination, ease of functionalization and modification have made this compound a ligand of choice in coordination chemistry [1,2,3], catalysis [4,5,6,7,8,9,10,11,12] and bioinorganic chemistry [13,14]. N-Functionalization is the simplest modification of PTA; it leaves the cage structure and the P-coordinating ability intact and affords a series of cationic species with tunable properties in terms of hydrophilicity and reactivity.…”

Section: Introductionmentioning

confidence: 99%

Pentafluorophenyl Platinum(II) Complexes of PTA and Its N-Allyl and N-Benzyl Derivatives: Synthesis, Characterization and Biological Activity

Sgarbossa

Śliwińska-Hill

ilva³

et al. 2019

Materials

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From the well-known 1,3,5-triaza-phosphaadamantane (PTA, 1a), the novel N-allyl and N-benzyl tetrafuoroborate salts 1-allyl-1-azonia-3,5-diaza-7-phosphaadamantane (APTA(BF4), 1b) and 1-benzyl-1-azonia-3,5-diaza-7-phosphaadamantane (BzPTA(BF4), 1c) were obtained. These phosphines were then allowed to react with (Pt(μ-Cl)(C6F5)(tht))2 (tht = tetrahydrothiophene) affording the water soluble Pt(II) complexes trans-(PtCl(C6F5)(PTA)2) (2a) and its bis-cationic congeners trans-(PtCl(C6F5)(APTA)2)(BF4)2 (2b) and trans-(PtCl(C6F5)(BzPTA)2)(BF4)2 (2c). The compounds were fully characterized by multinuclear NMR, ESI-MS, elemental analysis and (for 2a) also by single crystal X-ray diffraction, which proved the trans configuration of the phosphine ligands. Furthermore, in order to evaluate the cytotoxic activities of all complexes the normal human dermal fibroblast (NHDF) cell culture were used. The antineoplastic activity of the investigated compounds was checked against the human lung carcinoma (A549), epithelioid cervix carcinoma (HeLa) and breast adenocarcinoma (MCF-7) cell cultures. Interactions between the complexes and human serum albumin (HSA) using fluorescence spectroscopy and circular dichroism spectroscopy (CD) were also investigated.

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Section: Introductionmentioning

confidence: 99%

Pentafluorophenyl Platinum(II) Complexes of PTA and Its N-Allyl and N-Benzyl Derivatives: Synthesis, Characterization and Biological Activity

Sgarbossa

Śliwińska-Hill

ilva³

et al. 2019

Materials

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“…Today's chemistry of PTA covers complexes with the majority of transition metals . That progress initiated new studies aimed at further expanding PTA's functionality, including derivatization at the nitrogen and phosphorus atoms, substitutions at the methylene groups, and incorporation of new heteroatoms into the cage . Synthetic approaches to mono‐ and bicyclic ligands with the PTA‐like topology have also been explored .…”

Section: Introductionmentioning

confidence: 99%

Between Adamantane and Atrane: Intrabridgehead Interactions in the Cage‐Like Phosphane Related to a Novel Tris(homoadamantane) Ring System

Britvin

Rumyantsev

Zobnina

et al. 2016

Chemistry A European J

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Herein, we report unusual four-center interactions in the novel cage-like phosphane, 1,4,7-triaza-9-phosphatricyclo[5.3.2.1(4,9) ]tridecane (CAP). This water-soluble ligand, the first example of a tris(homoadamantane) ring system, can be considered a macrocyclic homologue of the well-known PTA (1,3,5-triaza-7-phosphaadamantane). However, (31) P NMR spectroscopic anomalies of CAP follow those typical for the bi-/tricyclic atrane systems. Another atrane-like feature of CAP is the ability of one nitrogen atom to undergo out-in pyramidal inversion. The latter is associated with a substantial decrease in the intracage N-N and P-N distances. Analysis of electron density distribution [molecular electrostatic potential (MESP) and atoms-in-molecules (AIM) approaches] suggests that the P and N atoms in the pyramidally inverted CAP derivatives are involved in interactions resulting in accumulation of electron density at the center of the phosphane cage. The latter can reliably explain the stereoelectronic and NMR anomalies of the new ligand. The semi-flexible CAP cage populates the structural niche between the rigid adamantine skeleton of PTA and flexible atrane systems and can be regarded as an alternative to PTA in aqueous coordination chemistry.

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“…Other synthetic strategies for P,C cage structures include cycloaddition reactions of phosphaalkynes with cyclobutadienes6 ( III ), thermolysis of 1,2,3‐tris(pentamethylcyclopentadienyl)cyclotriphosphene7 ( IV ) and reactions of triphosphabenzene with phosphenium salts8 ( V ). P,C cage structures containing other heteroatoms directly bound to phosphorus,9 such as oxygen10 and nitrogen,11 are also known. In contrast to P,C cages, for which ring expansions, rearrangements and coordination chemistry have been reported, related N,P,C systems have not been studied intensively due to a lack of facile synthetic protocols.…”

Section: Introductionmentioning

confidence: 99%

A Novel N,P,C Cage Complex Formed by Rearrangement of a Tricyclic Phosphirane Complex: On the Importance of Non‐covalent Interactions

Nesterov

Espinosa

Schnakenburg

et al. 2014

Chemistry A European J

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The reaction of Li/Cl P-CPh3 phosphinidenoid tungsten(0) complex 2 with dimethylcyanamide afforded tricyclic phosphirane complex 4, an unprecedented rearrangement of which led to the novel N,P,C cage complex 6. On the basis of DFT calculations, formation and intramolecular [3+2] cycloaddition of the transient nitrilium phosphane ylide complex 3 to a phenyl ring of the triphenylmethyl substituent to give 4 is proposed. Furthermore, theoretical evidence for terminal N-amidinophosphinidene complex 7, formed by [2+1] cycloelimination from 4, is provided, and the role of the electronic structure and non-covalent interactions of intermediate 7 discussed.

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Lower- and upper-rim-modified derivatives of 1,3,5-triaza-7-phosphaadamantane: Coordination chemistry and applications in catalytic reactions in water

Abstract: International audienceno abstrac

Cited by 24 publications

References 26 publications

Pentafluorophenyl Platinum(II) Complexes of PTA and Its N-Allyl and N-Benzyl Derivatives: Synthesis, Characterization and Biological Activity

Pentafluorophenyl Platinum(II) Complexes of PTA and Its N-Allyl and N-Benzyl Derivatives: Synthesis, Characterization and Biological Activity

Between Adamantane and Atrane: Intrabridgehead Interactions in the Cage‐Like Phosphane Related to a Novel Tris(homoadamantane) Ring System

A Novel N,P,C Cage Complex Formed by Rearrangement of a Tricyclic Phosphirane Complex: On the Importance of Non‐covalent Interactions

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