Syntheses of nonacarbonylbis(µ3-ethoxy)(µ2-halogeno)trimanganese complexes, the crystal structures of the fluoride and iodide, and the crystal structure of octacarbonyl(dimethylphenylphosphine)bis(µ3-ethoxy)(µ2-ethoxy)trimanganese

Abel, E. W.; Towle, I. D. H.; Cameron, T. Stanley; Cordes, Ruth E.

doi:10.1039/dt9790001943

Cited by 16 publications

(8 citation statements)

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“…Thus, in [Mn 3 -(CO) 9 (µ-OEt) 2 (µ-F)] 3 the fluorine bridge connecting two manganese atoms of a Mn 3 cluster is symmetric (within experimental error) but bent [Mn-F 1.93(2) and 1.97(2) Å; Mn-F-Mn 93(1)Њ]. 68 Other examples of basically symmetric bridges are provided by the fluoride complex of o-bis(chlorodimethyl-…”

Section: Symmetric Bent Bridgesmentioning

confidence: 85%

Fluorine as a structure-directing element in organometallic fluorides: discrete molecules, supramolecular self-assembly and host–guest complexation †

Roesky¹,

Haiduc²

1999

J. Chem. Soc., Dalton Trans.

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Section: Symmetric Bent Bridgesmentioning

confidence: 85%

Fluorine as a structure-directing element in organometallic fluorides: discrete molecules, supramolecular self-assembly and host–guest complexation †

Roesky¹,

Haiduc²

1999

J. Chem. Soc., Dalton Trans.

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“…In fact, we are aware of just one other related fluorocarbonylic complex structurally characterized. In [Mn 3 ( μ 2 -F)( μ 3 -OEt) 2 (CO) 9 ] the fluoro ligand bridges two manganese atoms separated by only 2.829(7) Å (Mn−F−Mn = 93(1)°) . However, the presence of a metal−metal bond in this trimetallic 52-valence-electron compound is doubtful.…”

Section: Resultsmentioning

confidence: 99%

Chemistry of Highly Electrophilic Binuclear Cations. 1. Oxidation Reactions of [M₂(η⁵-C₅H₅)₂(CO)₄(μ-Ph₂PCH₂PPh₂)] (M = Mo, W) with [FeCp₂]X (X = BF₄, PF₆)

Alvarez¹,

García²,

Garcı́a³

et al. 1999

Organometallics

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Oxidation of the title compounds with 2 equiv of [FeCp2]BF4 in dichloromethane leads to the tetracarbonylic fluoro complexes [M2Cp2(μ-F)(CO)4(μ-dppm)]BF4 in high yields (dppm = Ph2PCH2PPh2). By contrast, the analogous reaction with [FeCp2]PF6 gives the tricarbonylic fluoro derivatives [M2Cp2(μ-F)(μ-CO)(CO)2(μ-dppm)]PF6. Separate experiments revealed that the latter cations cannot be obtained through decarbonylation of the former fluoro complexes. By carrying out the [FeCp2]PF6 oxidations in the presence of halide ions X- (X = Cl, Br, I), the corresponding halo derivatives [M2Cp2(μ-X)(μ-CO)(CO)2(μ-dppm)]PF6 are formed in good yields. All above species are derived from the unsaturated dications [M2Cp2(μ-CO)2(CO)2(μ-dppm)]2+, which are the initial products of the removal of two electrons from the title compounds. Despite its high reactivity, the tungsten dication can be isolated as a solid, thanks to its low solubility in dichloromethane, and has been shown to react with other donor molecules such as acetate ions or methanol, to give tricarbonylic derivatives [W2Cp2(μ-Y)(μ-CO)(CO)2(μ-dppm)]PF6 (Y = O2CMe, OMe), which display structures comparable to those of the corresponding halogeno complexes. The structure of both tungsten fluoro complexes has been determined by X-ray diffraction methods, that on the tetracarbonylic compound revealing the presence of a weak H-bonding interaction between the BF4 - counterion and a methylenic hydrogen in the diphosphine ligand. The reaction pathways likely operative in the oxidation of the title compounds are analyzed in light of the experimental findings and the critical role played by the BF4 - or PF6 - counterions.

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“…Reactivity studies show that protonation is initiated by proton transfer and not by coordination of a lone pair of the conjugate base BF 4 -. 183 Hersh and Honeychuck described the preparation of the isostructural transition metal adducts mer-(cis-L)(trans-NO)(CO) 3 W(µ-F)EF n (EF n ) SbF 5 , L ) PMe 3 (202), PMe 2 Ph (203); PCy 3 (204); EF n ) BF 3 , L ) PMe 3 (205); EF n ) PF 5 , L ) PMe 3 (206)) from LW(CO) 5 and [NO][EF n+1 ] (Scheme 12). Within this series, thermal stability of the adducts decreases in the order SbF 6 -> BF 4 -> PF 6 -.…”

Section: A Chromiummentioning

confidence: 99%

Organometallic Fluorides: Compounds Containing Carbon−Metal−Fluorine Fragments of d-Block Metals

1997

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Syntheses of nonacarbonylbis(µ₃-ethoxy)(µ₂-halogeno)trimanganese complexes, the crystal structures of the fluoride and iodide, and the crystal structure of octacarbonyl(dimethylphenylphosphine)bis(µ₃-ethoxy)(µ₂-ethoxy)trimanganese

Cited by 16 publications

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Fluorine as a structure-directing element in organometallic fluorides: discrete molecules, supramolecular self-assembly and host–guest complexation †

Fluorine as a structure-directing element in organometallic fluorides: discrete molecules, supramolecular self-assembly and host–guest complexation †

Chemistry of Highly Electrophilic Binuclear Cations. 1. Oxidation Reactions of [M₂(η⁵-C₅H₅)₂(CO)₄(μ-Ph₂PCH₂PPh₂)] (M = Mo, W) with [FeCp₂]X (X = BF₄, PF₆)

Organometallic Fluorides: Compounds Containing Carbon−Metal−Fluorine Fragments of d-Block Metals

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Syntheses of nonacarbonylbis(µ3-ethoxy)(µ2-halogeno)trimanganese complexes, the crystal structures of the fluoride and iodide, and the crystal structure of octacarbonyl(dimethylphenylphosphine)bis(µ3-ethoxy)(µ2-ethoxy)trimanganese

Cited by 16 publications

References 0 publications

Fluorine as a structure-directing element in organometallic fluorides: discrete molecules, supramolecular self-assembly and host–guest complexation †

Fluorine as a structure-directing element in organometallic fluorides: discrete molecules, supramolecular self-assembly and host–guest complexation †

Chemistry of Highly Electrophilic Binuclear Cations. 1. Oxidation Reactions of [M2(η5-C5H5)2(CO)4(μ-Ph2PCH2PPh2)] (M = Mo, W) with [FeCp2]X (X = BF4, PF6)

Organometallic Fluorides: Compounds Containing Carbon−Metal−Fluorine Fragments of d-Block Metals

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Syntheses of nonacarbonylbis(µ₃-ethoxy)(µ₂-halogeno)trimanganese complexes, the crystal structures of the fluoride and iodide, and the crystal structure of octacarbonyl(dimethylphenylphosphine)bis(µ₃-ethoxy)(µ₂-ethoxy)trimanganese

Chemistry of Highly Electrophilic Binuclear Cations. 1. Oxidation Reactions of [M₂(η⁵-C₅H₅)₂(CO)₄(μ-Ph₂PCH₂PPh₂)] (M = Mo, W) with [FeCp₂]X (X = BF₄, PF₆)