“Through-space” 31P spin–spin couplings in ferrocenyl tetraphosphine coordination complexes: Improvement in the determination of the distance dependence of JPP constants

Hierso, Jean‐Cyrille; Evrard, David; Lucas, Dominique; Richard, Philippe; Cattey, Hélène; Hanquet, Bernard; Meunier, Philippe

doi:10.1016/j.jorganchem.2007.11.035

Cited by 28 publications

(19 citation statements)

References 19 publications

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“…Conversely, the solution 31 P NMR of 4 revealed a rare AA'BB' phosphorus spin system in which two pairs of P‐nuclei (central 1,1'‐P and peripheral 2,2'‐P) are magnetically inequivalent with strong mutual spin‐spin couplings. A large nuclear spin‐spin coupling ( J PP = 59 Hz, Figure ) related to the eclipsed mutual position of central phosphorus is conveyed by their lone pair sharing the same space in a proximity forced by the global conformation constraint , . Such non covalently bonding 31 P ··· 31 P nuclear spin TS J PP interactions occur through‐space, and since our work, have been widely recognized as a fairly common phenomenon in highly constrained dissymmetric diphosphines .…”

Section: Ferrocenyl Phosphinesmentioning

confidence: 56%

Highly Functionalized Ferrocenes

et al. 2020

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Ferrocene is unique among organometallic compounds, and serves notably as a versatile platform towards the production of ligands useful to promote transition metals chemistry. A general limiting aspect of the synthesis of ferrocene derivatives is the efficient access to sophisticated highly functionalized polysubstituted ferrocenes, i.e. bearing four or more substituents replacing hydrogen atoms on the cyclopentadienyl rings. These ferrocene derivatives can bear various functional or/and structuring spectator substituents. Their preparation involves synthetic difficulties resulting from the need of multiple functionalizations coexisting altogether, and satisfying functional group compatibility and high selectivity issues. In the last decades, our group initially designed highly functionalized polyphosphines and hybrid ligands (1,1′,3,3′-tetrafunctionalized

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Section: Ferrocenyl Phosphinesmentioning

confidence: 56%

Highly Functionalized Ferrocenes

et al. 2020

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“…21 For 4a and 4b, in contrast to constrained ferrocenyl tetraphosphine complexes, 8a,b rigid difluorocyclophanes, 22 or difluoronaphthalenes, 23 the distance separating P1•••P2 in the solid state is not directly correlated to the J SSCCs value observed in solution. Indeed, in the solid state, the molecular structure of 4b showed a separation distance d P1•••P2 = 6.9168 (8) Å between −Pi-Pr 2 and −PFu 2 groups which excludes (P, P′) lone-pairs overlap. Conversely, in solution, a strong TS spin−spin coupling J PP′ = 17 Hz is unambiguously observed.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…7 The application of nonbonded J PP SSCCs for the structural determination in solution of organophosphorus molecules including metallocenic fragments has been developed by our group using polyphosphino ferrocenes. 8 Nonbonded TS J PP couplings are useful for assessing the conformation of the ferrocene backbone in tri-and tetraphosphines, 8b because the orientation of the phosphino substituents hold on the ferrocene backbone can achieve efficient P-lone-pairs overlap (Figure 1, right). 8a When such overlap of electron lone pairs is achieved, the spin−spin coupling of magnetically equivalent spin active nuclei exists; however, it is not directly observable on the resulting NMR spectra.…”

Section: ■ Introductionmentioning

confidence: 99%

Unsymmetrically Substituted Bis(phosphino)Ferrocenes Triggering Through-Space ³¹(P, P′)-Nuclear Spin Couplings and Encapsulating Coinage Metal Cations

et al. 2021

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We describe unsymmetrically substituted di-tert-butylated 1,1'-bis(phosphino)ferrocenes, with phosphino substituents R = [5-methyl]-2-furyl = Fu, and R' = phenyl (4a), i-propyl (4b). A modular synthetic approach was applied from the di-tert-butylated ferrocene platform (1), which lead to the formation of new diphosphines by using 1,1'bis(diiodo)-3,3'-bis(tert-butyl)ferrocene (2) as synthetic precursor. In contrast to the cousin non-alkylated unsymmetrically substituted diphosphino-ferrocenes which were reported up to now, these diphosphines showed strong ( 31 P, P')nonbonded (" ug -p e") nuclear spin-spin coupling. The strength of such internuclear spin-spin coupling constant (SSCCs) J PP' ranges between 17 and 35 Hz, and as such, are not associated to traditional " ug -b d" 4 J PP. The characterizations of these ferrocene derivatives by X-ray diffraction in the solid state, and by multinuclear NMR in solution, evidence that the strong SSCCs are attributable to the conformational constraint which is imposed to ferrocene backbone by the introduction of alkyl substituents on this platform. The molecular structures resolved in the solid-state showed long P…P u u l ep up to 6.9168(8) Å, while in solution a (P, P')-phosphorus lone-pair overlap clearly occurs. This testifies to a sufficient degree of rotational flexibility of the alkylated ferrocene backbone. We examined the coordination chemistry of these diphosphines towards coinage metals: Cu, Ag and Au. The constraint unsymmetrically substituted diphosphines 4a and 4b allowed the selective formation of dinuclear two-coordinate linear gold(I) complexes with strong Au…Au aurophilic interactions. They also lead to rare tetrahedral homoleptic d 10 monocationic complexes, with all the coinage metals, by structuring the encapsulation of the cation in a highly constraint environment where the stacking interactions of the (hetero)aromatic substituents of the phosphino groups are decisive. The resulting AA'XX' 31 P NMR signature in solution of the complexes was simulated and analyzed, as well as the stacking interactions between the pairs of furyl rings that were illustrated by noncovalent interactions (NCI) computation.

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“…Also from the NMR analysis of several nickel and palladium halide complexes of a constrained ferrocenyl tetraphosphine, the existence in solution phase of unique 31 P-31 P ''through-space" nuclear spin-spin coupling constants (JPP) had been evidenced [78].…”

Section: Group Xb -Nipd Ptmentioning

confidence: 99%

Polydentate phosphines

Pascariu¹,

Iliescu²,

Popa³

et al. 2009

Journal of Organometallic Chemistry

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a b s t r a c tPhosphines are one of the most important classes of ligands in chemistry, in both the industrial and academic spheres. This review deals with the design and properties of polydentate phosphines, an original and broad class of multidentate ligands. The multidentate nature of these species has led to special properties, in which the spatial proximity of phosphorus atoms is crucial. The first part gives an overview of oligodentates polyphosphines in which is discussed the types and the basic routes for their synthesis. The review continues with the most important synthetic routes for obtaining complexes. Because of huge amount of literature data this review is not exhaustive, but it collects the most relevant findings in this area. The restriction to structural and spectroscopic properties allows us for a well organized handling of the complex material.

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“Through-space” 31P spin–spin couplings in ferrocenyl tetraphosphine coordination complexes: Improvement in the determination of the distance dependence of JPP constants

Cited by 28 publications

References 19 publications

Highly Functionalized Ferrocenes

Highly Functionalized Ferrocenes

Unsymmetrically Substituted Bis(phosphino)Ferrocenes Triggering Through-Space ³¹(P, P′)-Nuclear Spin Couplings and Encapsulating Coinage Metal Cations

Polydentate phosphines

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“Through-space” 31P spin–spin couplings in ferrocenyl tetraphosphine coordination complexes: Improvement in the determination of the distance dependence of JPP constants

Cited by 28 publications

References 19 publications

Highly Functionalized Ferrocenes

Highly Functionalized Ferrocenes

Unsymmetrically Substituted Bis(phosphino)Ferrocenes Triggering Through-Space 31(P, P′)-Nuclear Spin Couplings and Encapsulating Coinage Metal Cations

Polydentate phosphines

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Unsymmetrically Substituted Bis(phosphino)Ferrocenes Triggering Through-Space ³¹(P, P′)-Nuclear Spin Couplings and Encapsulating Coinage Metal Cations