A (Nitrido)chromium(V) Function Incorporated in a Keggin‐Type Polyoxometalate: [PW11O39CrN]5– – Synthesis, Characterization and Elements of Reactivity

Lahootun, Vanina; Karcher, Jeff; Courillon, Christine; Launay, Franck; Mijares, Kristopher; Maatta, Eric A.; Proust, Anna

doi:10.1002/ejic.200800609

Cited by 17 publications

(6 citation statements)

References 80 publications

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“… 49 This has been reported for the incorporation of first-row transition-metal cations, and we have also observed it in the metal nitrido derivatives [PW 11 O 39 MN] (10– n )– (M = Ru VI , Cr V ). 50 , 51 The ionic radius of the extra cation compared to that of W VI /Mo VI and its electronic configuration are likely relevant parameters, but the composition of the POM scaffold also appears to play a role: the IR spectra of K W Sn and K W9Mo2 Sn display a single ν(P–O) band at 1070 cm –1 (but a shoulder at 1055 cm –1 is present on the IR spectra of the postfunctionnalized species K W9Mo2 Sn [Fc] , whereas the ν(P–O) band is clearly split into two components at 1062 and 1035 cm –1 for K Mo Sn ( Figures S5, S8, and S11 ). 44 This suggests a decrease of the distortion from K Mo Sn to K W9Mo2 Sn and an increase of the robustness of the Sn insertion to what we are looking for.…”

Section: Resultsmentioning

confidence: 99%

When Identification of the Reduction Sites in Mixed Molybdenum/Tungsten Keggin-Type Polyoxometalate Hybrids Turns Out Tricky

et al. 2022

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The mixed molybdenum/tungsten Keggin-type polyoxometalate (POM) hybrid (TBA) 4 [PW 9 Mo 2 O 39 {Sn(C 6 H 4 I)}] (TBA = tert -butylammonium) has been prepared by the reaction between [α-PW 9 Mo 2 O 39 ] 7– and [Cl 3 Sn(C 6 H 4 I)] in dried acetonitrile, in the presence of tetra- n -butylammonium bromide. A further coupling reaction affords the ferrocenyl derivative (TBA) 4 [PW 9 Mo 2 O 39 {Sn(C 6 H 4 )C≡C(C 6 H 4 )Fc}]. The POM hybrids have been thoroughly characterized by NMR and IR spectroscopies. Electrochemical analysis confirms their ease of reduction compared to the all-W analogue, albeit with a second reduction process occurring at a lower potential than in the all-Mo species. It is noteworthy that the second reduction is accompanied by an unusual red shift of the electronic absorption spectrum. Whereas there is no doubt that the first reduction deals with Mo, the location of the second electron in the bireduced species, on the second Mo or on W, has thus been the subject of a cross-investigation by spectroelectrochemistry, electron spin resonance, and theoretical calculations. Finally, it came out that the second reduction is also Mo-centered with two unpaired and antiferromagnetically coupled extra electrons.

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Section: Resultsmentioning

confidence: 99%

When Identification of the Reduction Sites in Mixed Molybdenum/Tungsten Keggin-Type Polyoxometalate Hybrids Turns Out Tricky

et al. 2022

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“…Few metal nitrido derivatives of POMs have been synthesized. 93,94 Ru VI -nitrido with Keggin anions has been predicted theoretically to be stable and electrophilic. [95][96][97] 14) (X = Si or Ge) reveals monomeric complexes with highly unusual vicinal terminal Ru VI -nitrido units.…”

Section: Ru VI -Nitrido Complexesmentioning

confidence: 99%

Recent developments in ruthenium nitrido complexes

Liang

2013

RSC Adv.

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Metal nitrido complexes are frequently invoked as key intermediates in numerous synthetic, catalytic and enzymatic transformations, such as C-N and H-N bond-formation, nitrogen atom/group transfer reactions and biological nitrogen fixation by nitrogenase enzyme. Ruthenium nitrido complex is one of the most important metal nitrido complexes. There is a growing interest in chemistry of Ru-nitride. Over the past decade, numerous chemically activated ruthenium nitrido complexes have been discovered. This short review summarizes recent advances in the synthesis and reactivity of these complexes.

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“…Polyoxometalates (POMs) display unique properties as ligands. − They are able to stabilize both low- and high-oxidation metal states, and like porphyrins and corroles, , they can accommodate metal nitrido functions, as documented in our recent reports (M = Re, Cr, Ru, − M = Mn). There is now both experimental and theoretical evidence for the influence of POMs on the reactivity of high-valent metal−nitrido bonds.…”

Section: Introductionmentioning

confidence: 96%

Addition of N-Heterocyclic Carbenes to a Ruthenium(VI) Nitrido Polyoxometalate: a New Route to Cyclic Guanidines

et al. 2011

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The scope of N-atom transfer from the electrophilic ruthenium(VI) nitrido containing polyoxometalate [PW(11)O(39)Ru(VI)N](4-) has been extended to the N-heterocyclic carbene {CH(2)(Mes)N}(2)C and the coupling product {CH(2)(Mes)N}(2)CNH(2)(+) characterized by (1)H NMR and high-resolution mass spectrometry. Because guanidines display many fields of applications ranging from biology to supramolecular chemistry, this could afford an original route to the synthesis of cyclic guanidines. This also enlarges the potential of nitrido complexes in the synthesis of heterocycles, mainly illustrated in the literature through the formation of aziridines through N-atom transfer to alkenes. In the course of the reaction, the ruthenium(III)-containing polyoxometallic intermediate [PW(11)O(39)Ru(III){NC{N(Mes)CH(2)}(2)}](5-) has been thoroughly characterized by continuous-wave and pulsed electron paramagnetic resonance, which nicely confirms the presence of the organic moiety on the polyoxometallic framework, Ru K-edge X-ray absorption near-edge structure, and electrochemistry.

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A (Nitrido)chromium(V) Function Incorporated in a Keggin‐Type Polyoxometalate: [PW₁₁O₃₉CrN]^5– – Synthesis, Characterization and Elements of Reactivity

Cited by 17 publications

References 80 publications

When Identification of the Reduction Sites in Mixed Molybdenum/Tungsten Keggin-Type Polyoxometalate Hybrids Turns Out Tricky

When Identification of the Reduction Sites in Mixed Molybdenum/Tungsten Keggin-Type Polyoxometalate Hybrids Turns Out Tricky

Recent developments in ruthenium nitrido complexes

Addition of N-Heterocyclic Carbenes to a Ruthenium(VI) Nitrido Polyoxometalate: a New Route to Cyclic Guanidines

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