Janus bis(NHCs) tuned by heteroatom-bridge oxidation states

Naz, Nabila Rauf; Schnakenburg, Gregor; Mikeházi, Antal; Kelemen, Zsolt; Nyulászi, László; Boeré, René T.; Streubel, Rainer

doi:10.1039/c9cc08468a

Cited by 13 publications

(14 citation statements)

References 54 publications

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“…To get access to the desired (unsaturated) 1,4-diphosphinine 10f, an isomeric mixture of 9f was treated with n Bu 3 P (Scheme 6), following our previously established protocol. 19,29 Despite the observed formation of the resulting phosphonium salt, the 31 P{ 1 H} NMR spectrum of the dark brown reaction mixture did not show any resonance attributable to the targeted product (calculated 31 To get some insight into the bonding of 10d DFT calculations were performed which indicated a closed shell singlet ground state, with a notably small HOMO/LUMO gap (2.23 eV). The latter gap is much smaller compared to the tricyclic 1,4diphosphinines, reported earlier by us (Table 6).…”

Section: Dalton Transactions Papermentioning

confidence: 99%

Access to and reactions of P-functional 1,4-dihydro-1,4-diphosphinines fused to two TTF units

Kermanshahian¹,

Kalisch²,

Kelemen³

et al. 2023

Dalton Trans.

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Section: Dalton Transactions Papermentioning

confidence: 99%

Access to and reactions of P-functional 1,4-dihydro-1,4-diphosphinines fused to two TTF units

Kermanshahian¹,

Kalisch²,

Kelemen³

et al. 2023

Dalton Trans.

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“…The stability of the anionic state was found to be higher in the case of the thiazolethione derivative . It was also noteworthy that P-bridged, tunable bis(N-heterocyclic carbenes) could also be synthesized, , but the attempted desulfurization of the thione XI itself was unsuccessful …”

Section: Introductionmentioning

confidence: 99%

“…The stability of the anionic state was found to be higher in the case of the thiazolethione derivative. 18 It was also noteworthy that P-bridged, tunable bis(N-heterocyclic carbenes) could also be synthesized, 19,20 but the attempted desulfurization of the thione XI itself was unsuccessful. 20 As a logical extension of our previous work, we decided to attempt the synthesis of XV, which (with R′ = Cl) would be a precursor of the aromatic(?)…”

Section: ■ Introductionmentioning

confidence: 99%

Toward a 1,4-Diphosphinine-Based Molecular CPS-Ternary Compound

et al. 2021

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Synthesis of the tricyclic 1,3-dithiole-2-thione-derived 1,4-dihydro-1,4-diphosphinine is presented using a base-induced ring formation protocol and chloro(diethylamino)(1,3-dithiole-2-thion-4-yl)phosphane as the starting point. P-oxidation reactions of dihydrodiphosphinine by chalcogens led to bis(P-oxide), bis(P-sulfide), or bis(P-selenide), respectively; all tricyclic compounds were obtained as cis/trans mixtures. 1,4-Dihydro-1,4-diphosphinine was converted into 1,4-dichloro-1,4-dihydro-1,4-diphosphinine. This compound is almost insoluble in organic solvents, furnished selectively the trans-bis(amino) derivative upon a 2-fold P-substitution reaction with the weak nucleophile potassium bis(trimethylsilyl)amide, and reacted also with alcohols ROH (R = nBu, iPr, tBu) to give cis/trans mixtures of the corresponding bis(alkoxy) derivatives. Furthermore, the dichloro derivative could be reduced to a 1,4-diphosphinine using PnBu3, but, unfortunately, the stubbornly insoluble product could be neither purified nor crystallized. Despite this, we achieved a thermal [4 + 2] cycloaddition reaction of this first CPS-ternary compound with diethylacetylene dicarboxylate to obtain the corresponding diphosphabarrelene, thus providing indirect evidence for the aromatic tricyclic diphosphinine. Detailed density functional theory studies on the formation of 1,4-diphosphinine provided insights into formation pathways as well as NMR, IR, and UV/vis data.

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“…Cyclic voltammetry can be used to quantify metalto-metal interactions in homobimetallic complexes with ditopic NHC ligands, [56][57][58][59] but is difficult to apply to bis-gold complexes. 5,6 In a preliminary cyclic voltammetry (CV) study of the BBI-based bis-gold(I) homobimetallic complex 6, we observed that none of the Au I centers (inside or outside the CD cavity) were oxidized under the conditions used, although the outside Au I center could be chemically oxidized to give complex 12. Additional CV experiments starting from the Au III complexes 12-14 suggested that the nature of the encapsulated metal in the cavity (Au I , Ag I or Cu I ) had no significant influence on the Au III /Au I reduction potential of the gold center outside the cavity (see ESI †), a similar trend to that observed by NMR for the C carbene chemical shifts.…”

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confidence: 99%