Synthesis and Chemical and Electrochemical Characterization of Fe−S Carbonyl Clusters. X-ray Crystal Structures of [N(PPh3)2]2[Fe5S2(CO)14] and [N(PPh3)2]2[Fe6S6(CO)12]

Calderoni, Francesca; Demartin, Francesco; Iapalucci, Maria Carmela; Laschi, Franco; Longoni, Giuliano; Zanello, Piero

doi:10.1021/ic950482t

Cited by 30 publications

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“…In Homoleptic carbonyl transition metal clusters show little propensity for multiple redox changes. [1Ϫ3] Only some ex-other cases, such as [Co 13 C 2 (CO) 30 ] nϪ and [Co 9 Si(CO) 23 ] nϪ , a synergy between steric (good fit of the cavity) and elecceptional compounds feature different (three or more) oxidation states which are stable, or sufficiently long-lived, to tronic (extra-stabilisation arising from CoϪC or CoϪSi bonds) effects seems to be operative. permit isolation or spectroscopic characterisation of the species.…”

Section: Introductionmentioning

confidence: 99%

“…In particular Fe 8 (CO) 32 ] nϪ (n ϭ 3, 4, 5), [7] and [AuFe 4 (CO) 16 ] nϪ (n ϭ 1, the former two homometallic clusters undergo two consecu-2, 3); [8] a few more associate group 14Ϫ16 elements, e.g. tive pairs of close-spaced one-electron reductions, as well as [Co 13 C 2 (CO) 30 ] nϪ (n ϭ 3, 4, 5, 6), [9,2c] [Co 9 Si(CO) 23 ] nϪ (n ϭ two close-spaced one-electron oxidations. Several of the 2, 3, 5), [10] [Ni 11 Bi 2 (CO) 18 ] nϪ (n ϭ 2, 3, 4), [11] above redox changes display features of electrochemical re-[Ni 13 Sb 2 (CO) 24 ] nϪ (n ϭ 2, 3, 4), [12] and [Fe 5 S 2 (CO) 14 ] nϪ versibility, even if most electrogenerated species are only (n ϭ 0, 1, 2), [13] in their cluster cores.…”

Section: Introductionmentioning

confidence: 99%

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Electron-Sink Behaviour of the Carbonylnickel Clusters [Ni32C6(CO)36]6– and [Ni38C6(CO)42]6–: Synthesis and Characterization of the Anions [Ni32C6(CO)36]n– (n = 5–10) and [Ni38C6(CO)42]n– (n = 5–9) and Crystal Structure of [PPh3Me]6[Ni32C6(CO)36] · 4 MeCN

Calderoni

Demartin

Biani

et al. 1999

Eur. J. Inorg. Chem.

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The hexacarbide clusters [H6–nNi38C6(CO)42]n− (n = 3, 4, 5, or 6) have been directly obtained from the reaction of [Ni6(CO)12]2– with C3Cl6, whereas the related anions, [H6–nNi32C6(CO)36]n− (n = 5 or 6), have been obtained by degradation under carbon monoxide of [Ni38C6(CO)42]6–, or upon thermal treatment at ca. 110 °C of [Ni10C2(CO)16]2– salts. The compound [PPh3Me]6[Ni32C6(CO)36] ·4 MeCN is triclinic, space group P&1macr; (No 2), with a = 15.974(3), b = 17.474(3), c = 18.200(4) Å, α = 61.37(2), β = 69.31(2), γ = 72.35(2)° and Z = 1; final R = 0.033. The structure of [Ni32C6(CO)36]6– has an idealised Oh symmetry and is based on a truncated octahedral Ni32C6 framework, with all edges spanned by bridging carbonyl groups. The six interstitial carbide atoms are lodged in square‐antiprismatic cavities. The overall geometry of the Ni32C6 core is very similar to that found previously in [HNi38C6(CO)42]5–, and shows very close interatomic separations. Both [Ni32C6(CO)36]6– and [H6–nNi38C6(CO)42]n− (n = 5 or 6) display electron‐sink behaviour. Thus, they have been chemically and electrochemically reduced to their corresponding [Ni32C6(CO)36]n− (n = 7–10), [Ni38C6(CO)42]n− (n = 7–9) and [HNi38C6(CO)42]n− (n = 6–8) derivatives, and several of the involved redox changes show features of electrochemical reversibility. In contrast, both [Ni32C6(CO)36]6– and [H6–nNi38C6(CO)42]n− (n = 5 or 6) support only one partially reversible oxidation step. Their different behaviour upon protonation or oxidation is an indirect, but unambiguous, proof of the hydride nature of [HNi32C6(CO)36]5– and [H6–nNi38C6(CO)42]n− (n = 3, 4, or 5), which could not be validated by 1H‐NMR spectroscopy.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Electron-Sink Behaviour of the Carbonylnickel Clusters [Ni32C6(CO)36]6– and [Ni38C6(CO)42]6–: Synthesis and Characterization of the Anions [Ni32C6(CO)36]n– (n = 5–10) and [Ni38C6(CO)42]n– (n = 5–9) and Crystal Structure of [PPh3Me]6[Ni32C6(CO)36] · 4 MeCN

Calderoni

Demartin

Biani

et al. 1999

Eur. J. Inorg. Chem.

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“…[{Fe(ox-phS) 2 [18] [{Fe(Fe 2 S 2 CO 6 )} 2 (µ-S) 2 ] 2-S 4 2.198(2) NA [a] 2.675(2) 104.96 (7) 74.98(7) [19] [{FeCl 2 } 2 (µ-S) 2 ] [17] [a] NA = not available. (Table 3), confirming previous studies where the {Fe 2 S 2 } core was found nearly invariant to the nature of the terminal ligands.…”

Section: Synthesis and X-ray Diffraction Analyses Of Products 1-3mentioning

confidence: 99%

“…(Table 3), confirming previous studies where the {Fe 2 S 2 } core was found nearly invariant to the nature of the terminal ligands. [17][18][19] It is known from the literature that the reaction of FeCl 3 with dithiols, hydrogen sulfide and sodium methoxide in methanol affords the dimeric Fe…”

Section: Synthesis and X-ray Diffraction Analyses Of Products 1-3mentioning

confidence: 99%

Redox Processes Involved in the Synthesis and Reactivity of Oxazolinylthiophenolato Complexes of Iron(II)/(III)

et al. 2010

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The reaction of anhydrous FeCl2 with 2‐(4′,4′‐dimethyloxazolin‐2′‐yl)thiophenolate (ox‐phS–) afforded mononuclear [Fe(ox‐phS)2] (A) and binuclear [{FeIII(ox‐phS)}2(μ‐S)2] (B). In B, iron(III) and S2– resulted from an unexpected redox reaction involving elemental sulfur and the iron(II) starting material. Complexes A and B co‐crystallise reproducibly in a 2:1 proportion. An attempt to prepare (oxazolinylthiophenolato)iron(III) from Li(ox‐phS) and anhydrous FeCl3 in the presence of N,N,N′,N′‐tetramethylethane‐1,2‐diamine (tmen) gave another redox reaction with disulfide D, bis{2‐(4′,4′‐dimethyloxazolin‐2′‐yl)phenyl}disulfide (ox‐phS‐Sph‐ox), and trans‐[FeCl2(tmen)2] (E) as 1:1 co‐crystallised products. Characterisation of all complexes included Mössbauer spectroscopy and single‐crystal X‐ray diffraction analysis. Quantum mechanical (TDDFT) calculations for A and cyclic voltammetry experiments carried out with A and C helped to distinguish between ligand‐ and metal‐based electronic transitions and redox processes. Results add to the knowledge of the rich redox chemistry of early transition metals with soft S‐donor ligands, with possible consequences for catalytic and biochemical transformations.

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“…Both compounds form a 14-membered ring. The clusters consist of a central [Fe 6 A C H T U N G T R E N N U N G (m 3 -S) 6 (CO) 12 12 ] 2À core has been reported previously as ammonium or bis(triphenylphosphine)iminium salts, which were prepared in a much different way starting from the iron-sulfur-carbonyl dianions [Fe 3 S(CO) 9 ] 2À , [23] [Fe 5 S 4 (CO) 12 ] 2À , [24] or K 2 S 4 . [25] A coordina-tion of the [Fe 6 S 6 (CO) 12 ] 2À core to another metal is so far not known.…”

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confidence: 99%

Wheel‐Shaped Lanthanide Iron Sulfide Clusters

Konchenko

Sanden

Pushkarevsky

et al. 2010

Chemistry A European J

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Synthesis and Chemical and Electrochemical Characterization of Fe−S Carbonyl Clusters. X-ray Crystal Structures of [N(PPh₃)₂]₂[Fe₅S₂(CO)₁₄] and [N(PPh₃)₂]₂[Fe₆S₆(CO)₁₂]

Cited by 30 publications

References 31 publications

Electron-Sink Behaviour of the Carbonylnickel Clusters [Ni32C6(CO)36]6– and [Ni38C6(CO)42]6–: Synthesis and Characterization of the Anions [Ni32C6(CO)36]n– (n = 5–10) and [Ni38C6(CO)42]n– (n = 5–9) and Crystal Structure of [PPh3Me]6[Ni32C6(CO)36] · 4 MeCN

Electron-Sink Behaviour of the Carbonylnickel Clusters [Ni32C6(CO)36]6– and [Ni38C6(CO)42]6–: Synthesis and Characterization of the Anions [Ni32C6(CO)36]n– (n = 5–10) and [Ni38C6(CO)42]n– (n = 5–9) and Crystal Structure of [PPh3Me]6[Ni32C6(CO)36] · 4 MeCN

Redox Processes Involved in the Synthesis and Reactivity of Oxazolinylthiophenolato Complexes of Iron(II)/(III)

Wheel‐Shaped Lanthanide Iron Sulfide Clusters

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