Organometallic sulfur complexes. XIII. Synthesis, structure, and bonding of a new metal-sulfur cluster system, tris(cyclopentadienylnickel) disulfide. The influence of valence electrons on molecular geometry

Vahrenkamp, Heinrich; Uchtman, Vernon A.; Dahl, Lawrence F.

doi:10.1021/ja01014a071

Cited by 85 publications

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“…The same architecture was found for the isoelectronic complexes [Ni 3 S 2 (PEt 3 ) 6 ] 2+[25] and [Ni 3 S 2 (PPh 3 ) 4 Cl 2 ] 26. Compound [Ni 3 S 2 Cp 3 ]27 contains the trigonal‐bipyramidal [Ni 3 S 2 ] unit. The Ni–Ni distances in 5b [282.9(3) pm] are significantly shorter than in [Ni 3 S 2 (PEt 3 ) 6 ] 2+ [291.0(2) pm] and [Ni 3 S 2 (PPh 3 ) 4 Cl 2 ] [289.5(2)–293.4(2) pm], but comparable with the Ni–Ni distancesin [Ni 3 S 2 Cp 3 ] [280.1(5) pm].…”

Section: Resultsmentioning

confidence: 99%

Syntheses, Structures and Magnetic Properties of New Chalcogen‐Bridged Heterodimetallic Cluster Compounds with Heterocubane Structure

Bechlars

Issac

Feuerhake³

et al. 2008

Eur J Inorg Chem

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The reaction of nickel, iron and cobalt complexes with MCl5 (M = Nb, Ta) and silylated chalcogen compounds in the presence of phosphane ligands yield the cluster compounds [Nb2Ni2S4Cl4(PPh3)2(CH3CN)2] (1), [Nb2Ni2Se4Cl4(PPh3)2(CH3CN)2] (2), [Ta2Ni2S4Br4(PPh3)2(CH3CN)2] (3), [Ta2Ni2Se4Br4(PPh3)2(CH3CN)2] (4), [Ni3S2(PMe3)6][Ta3NiS4(PMe3)4Cl6]2 (5), [Fe(dppm)2(CH3CN)2][NbFe3S4Cl3(dppm)(CH3CN)]2 (6) [dppm = (diphenylphosphanyl)methane], [Fe(dppm)2(CH3CN)2][TaFe3S4Cl3(dppm)(CH3CN)]2 (7), [FeCl(dppmSe)2][TaFe3Se4Cl3(dppm)(CH3CN)] (8) and [NbCo3Se4(PPh3)3(CH3CN)3][CoCl3(PPh3)] (9). The compounds (Et4N)3[NbFe2S4(SPh)4] (10) and (Et4N)3[NbFe2Se4(SPh)4] (11) were obtained by treating (Et4N)2[Fe(SPh)4] with Li3NbE4 (E = S, Se). (Et4N)3[Nb2Fe6S8(SPh)9] (12) was synthesized by adding FeCl2 to compound 10 used as starting material. (Et4N)3[Nb2Fe6Se8(SePh)9] (13) (which is isostructural to 12) was synthesized by treating FeCl2 with NaSetBu, NbCl5 and PhSeSiMe3. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Section: Resultsmentioning

confidence: 99%

Syntheses, Structures and Magnetic Properties of New Chalcogen‐Bridged Heterodimetallic Cluster Compounds with Heterocubane Structure

Bechlars

Issac

Feuerhake³

et al. 2008

Eur J Inorg Chem

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“…When the oxygenation reaction of 2 was conducted in dichloromethane together with an excess of HMPA, the solution was found to be a mixture of both Fe(N03)(Cl)2(HMPA)2 (7) and Fe(N03)2(Cl)(HMPA)2 ( 8), as was easily demonstrated through independent preparations of these two complexes from anhydrous iron(III) chloride, HMPA, and silver nitrate in acetonitrile.…”

Section: Resultsmentioning

confidence: 85%

“…When conducted in the presence of 2 equiv of HMPA per iron atom in dichloromethane or acetonitrile at room temperature, the oxygenation of [Fe(NO)2(Cl)]2 yielded exclusively Fe(N03)2-(C1)(HMPA)2 (7). This reaction, which affords a bis(nitrato) complex, compares well with the oxidation of [Fe(NO)2(Cl)]2 by (7) Hartmann, J. R.; Rardin, R. L.; Chaudhuri, P.; Pohl, K.; Wieghardt, K.; Nuber, B.; Weiss, J.; Papaefthymiou, G. C.; Frankel, R. B.; Lippard, S. J. J. Am.…”

Section: Resultsmentioning

confidence: 99%

“…We have found3 that the iron-nitrato-iron-nitrosyl couple could constitute a new alternative for the activation and transfer of molecular oxygen; the nitrosyl ligands in the dinitrosyliron dimers Fe(Cl)3(HMPA)-72HMPA (5) 25.08 Fe(N03)2(Cl)(HMPA)2 (7) 25.12 6.33 [Fe(NO)2X]2 (X = Cl, I) are oxidized by molecular oxygen, in the presence of PPh3 or OPPh3, to nitrato and not nitro ligands, from which oxygen is then transferred to phosphines and olefins. However, such oxidizable ligands as phosphines are not likely to produce long-lived active species; furthermore, the nitrosyl species in the couple was found to encounter side reactions leading to the termination of the catalytic cycle in this system.…”

Section: Introductionmentioning

confidence: 99%

“…Oxidation by oxygen (1 atm) of the Fe-NO moiety in 2, 3, or 1 in the presence of HMPA results in the formation of the nitrato-and not nitro-complexes Fe(N03)(Cl)2(HMPA). '/2HMPA (4), Fe(N03)2(Cl)(HMPA)-'/2HMPA (6), Fe(N03)2(Cl)(HMPA)2 (7) and Fe(N03)(Cl)2-(HMPA)2 (8). The molecular structure of 8 has been determined by X-ray diffraction.…”

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The iron-nitrato/iron-nitrosyl couple in the presence of hexamethylphosphoric triamide and its relevance to oxygen activation and transfer. X-ray structure of Fe(NO3)(Cl)2(HMPA)2

Wah¹,

Postel²,

Tomi³

1989

Inorg. Chem.

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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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Organometallic sulfur complexes. XIII. Synthesis, structure, and bonding of a new metal-sulfur cluster system, tris(cyclopentadienylnickel) disulfide. The influence of valence electrons on molecular geometry

Cited by 85 publications

References 0 publications

Syntheses, Structures and Magnetic Properties of New Chalcogen‐Bridged Heterodimetallic Cluster Compounds with Heterocubane Structure

Syntheses, Structures and Magnetic Properties of New Chalcogen‐Bridged Heterodimetallic Cluster Compounds with Heterocubane Structure

The iron-nitrato/iron-nitrosyl couple in the presence of hexamethylphosphoric triamide and its relevance to oxygen activation and transfer. X-ray structure of Fe(NO3)(Cl)2(HMPA)2

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

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