Hydrothermal synthesis and solid-state structure of Tc2(μ-O2CCH3)4Cl2

Kerlin, William M.; Poineau, Frédéric; Czerwinski, Kenneth R.; Forster, Paul M.; Sattelberger, Alfred P.

doi:10.1016/j.poly.2012.09.064

Cited by 8 publications

(7 citation statements)

References 10 publications

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“…Historically, Tc 2 (O 2 CCH 3 ) 4 Cl 2 was the first dinuclear technetium complex coordinated to acetate ligands to be reported. [14][15] This compound was synthesized by treating potassium pertechnetate (KTcO 4 ) in an acetic acid/HCl mixture at 210 ºC in large stainless steel autoclaves that were pressurized to 30 atm with hydrogen gas. In these earlier preparations, the autoclaves corroded rapidly upon exposure to the hot concentrated mineral acid.…”

Section: Preparation Of Tc 2 (O 2 Cch 3 ) 4 I and K[tc 8 (μ-I) 8 I 4 ]Imentioning

confidence: 99%

“…In the latter compound, the Re-Re separation is 2.229(3) Å and the Re-Cl-Re angle is 134º. [29] In (2.1785(3) Å) [15] and Tc 2 (O 2 CCMe 3 ) 4 Cl 2 (2.192(2) Å). [30] This phenomenon is likely due to stronger metal-metal  bonding in the Tc 2 5+ core than in the Tc 2 6+ core as was previously discussed for the Tc 2 X 8 n-(n = 2, 3; X = Cl, Br) systems.…”

Section: Structure and Magnetic Properties Of [Tc 2 (μ-O 2 Cch 3 ) 4 ]Imentioning

confidence: 99%

“…[9,10] The study of Tc 2 (O 2 CCH 3 ) 2 Cl 4 also permitted to better understand the influence of acetate ligand on the Tc-Tc bonding. [11] Currently, only five compounds containing a Tc 2 n+ (n = 5, 6) units coordinated to acetate and halogen ligands are structurally characterized: Tc 2 (O 2 CCH 3 ) 4 X [12,13] , K[Tc 2 (O 2 CCH 3 ) 4 Cl 2 ] and Tc 2 (O 2 CCH 3 ) 4 X 2 (X = Cl, Br), [14,15] and no complexes with multiple metal-metal bonds coordinated to iodide ligands have been reported yet. H 2 O 2 .…”

Section: Introductionmentioning

confidence: 99%

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Hydrothermal synthesis and solid-state structures of polynuclear technetium iodide compounds

Kerlin

Poineau

Forster

et al. 2015

Inorganica Chimica Acta

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Two new technetium iodide compounds, Tc 2 (O 2 CCH 3 ) 4 I and K[Tc 8 (μ-I) 8 I 4 ]I, were synthesized in an autoclave from the reaction of KTcO 4 in glacial acetic acid with hydroiodic acid and/or alkali metal iodide salts at 210 ºC under 60-70 atm hydrogen pressure. The structures of Tc 2 (O 2 CCH 3 ) 4 I and K[Tc 8 (μ-I) 8 I 4 ]I were solved by single-crystal X-ray diffraction. The compound Tc 2 (O 2 CCH 3 ) 4 I crystallizes in the monoclinic space group C2/m with a = 7.1194(6) Å, b = 14.5851(13) Å, c = 7.1586(6) Å, and β = 110.9540(10)º. The structure of Tc 2 (O 2 CCH 3 ) 4 I consists of infinite chains of Tc 2 (O 2 CCH 3 ) 4 + units linked by bridging iodides, an arrangement similar to the one found in Tc 2 (O 2 CCH 3 ) 4 X (X = Cl, Br). The Tc-Tc separation in Tc 2 (O 2 CCH 3 ) 4 I (i.e., 2.1146(4) Å) is consistent with the presence of a Tc-Tc bond of order 3.5. Magnetic susceptibility measurements reveal Tc 2 (O 2 CCH 3 ) 4 I to be paramagnetic (μ eff = 1.84 B.M.) and support the electronic configuration        1 for the Tc 2 5+ unit in the compound. The compound K[Tc 8 (μ-I) 8 I 4 ]I crystallizes in the monoclinic space group P2 1 /n with a = 8.0018(5) Å, b = 14.5125(10) Å, c = 13.1948(9) Å, and β = 102.3090(10)º, and is the first octanuclear technetium iodide cluster to be reported. The Tc-Tc separations in the [Tc 8 (μ-I) 8 I 4 ] cluster (i.e., 2.164(3) Å, 2.5308(8) Å and 2.72(3) Å) suggest the presence of Tc≡Tc triple bonds, Tc=Tc double bonds and Tc-Tc single bonds.

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Section: Preparation Of Tc 2 (O 2 Cch 3 ) 4 I and K[tc 8 (μ-I) 8 I 4 ]Imentioning

confidence: 99%

Section: Structure and Magnetic Properties Of [Tc 2 (μ-O 2 Cch 3 ) 4 ]Imentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Hydrothermal synthesis and solid-state structures of polynuclear technetium iodide compounds

Kerlin

Poineau

Forster

et al. 2015

Inorganica Chimica Acta

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“…Tc 2 (O 2 CCH 3 ) 4 Cl 2 can be synthesized by two methods: (1) treatment of a solution of KTcO 4 with a 2:1 mixture of acetic acid and concentrated aqueous hydrochloric acid under excess hydrogen for 14 h at 210 °C in an autoclave12 [Equation (2)]; (2) reaction of ( n Bu 4 N) 2 Tc 2 Cl 8 in a mixture of acetic acid and acetic anhydride (vol/vol 4:1) heated to reflux for 5 min [Equation (3)] 13 …”

Section: Complexes With the Tc26+ Units: Study Of (Nbu4n)2tc2x8 (Xmentioning

confidence: 99%

“…Single crystals of Tc 2 (O 2 CCH 3 ) 4 Cl 2 were obtained by using the autoclave method. The complex Tc 2 (O 2 CCH 3 ) 4 Cl 2 crystallizes in the monoclinic space group P 2 1 / n with cell parameters a = 6.4258(8) Å, b = 8.8474(11) Å, c = 12.5285(16) Å, and β = 90.778(2)°, and is isostructural with Re 2 (O 2 CCH 3 ) 4 Cl 2 12. The compound (Figure 2) exhibits the paddlewheel motif and consists of four trans ‐acetate ligands bridging the Tc 2 6+ unit and two axial terminal chlorides.…”

Section: Complexes With the Tc26+ Units: Study Of (Nbu4n)2tc2x8 (Xmentioning

confidence: 99%

A Decade of Dinuclear Technetium Complexes with Multiple Metal–Metal Bonds

et al. 2014

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Transition metal complexes with multiple metal–metal bonds exhibit interesting catalytic and biological properties. One element whose metal–metal bond chemistry has been poorly studied is technetium. Currently, only 25 technetium complexes with multiple metal–metal bonds have been structurally characterized. The nature of metal–metal interactions in these complexes, as well as the influence of ligands on the bonding in the Tc2n+ unit (n = 6, 5, 4) are not well understood. In order to better understand the influence of ligands on the Tc–Tc bonding, a study of the solid‐state and electronic structure of dinuclear complexes with the Tc2n+ unit (n = 6, 5, 4) has been performed. Dinuclear technetium complexes (nBu4N)2Tc2X8, Tc2(O2CCH3)4X2, Tc2(O2CCH3)2Cl4, cesium salts of Tc2X83–, and Tc2X4(PMe3)4 (X = Cl, Br) were synthesized; their molecular and electronic structures, as well as their electronic absorption spectra, were studied by a number of physical and computational techniques. The structure and bonding in these systems have been investigated by using multiconfigurational quantum calculations. For all these complexes, the calculated geometries are in very good agreement with those determined experimentally. Bond order analysis demonstrates that all these complexes exhibit a total bond order of approximately 3. Analysis of individual effective bond order (EBO) components shows that these complexes have similar σ components, while the strength of their π components follows the order Tc2X4(PMe3)4 > Tc2X83– > Tc2(O2CCH3)2Cl4 > Tc2X82–. Calculations indicate that the δ components are the weakest bond in Tc2X8n– (n = 2, 3) and Tc2(O2CCH3)2Cl4. Further analysis of Tc2X83– and Tc2X4(PMe3)4 (X = Cl, Br) indicates that the electronic structure of the Tc25+ and Tc24+ units is insensitive to the nature of the coordinating ligands. The electronic absorption spectra of Tc2X8n– (n = 2, 3), Tc2(O2CCH3)2Cl4, and Tc2X4(PMe3)4 (X = Cl, Br) were studied in solution, and assignment of the transitions was performed by multiconfigurational quantum chemical calculations. For the Tc2X8n– (n = 2, 3; X = Cl, Br) anions and Tc2(O2CCH3)2Cl4, the lowest‐energy band is attributed to the δ→δ* transition. For Tc2X4(PMe3)4, the assignment of the transitions follow the following order in energy: δ*→σ* < δ*→π* < δ→σ* < δ→π*.

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Group 7 Metal–Metal Bonds

Poineau

Sattelberger

et al. 2015

Molecular Metal‐Metal Bonds

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Hydrothermal synthesis and solid-state structure of Tc2(μ-O2CCH3)4Cl2

Cited by 8 publications

References 10 publications

Hydrothermal synthesis and solid-state structures of polynuclear technetium iodide compounds

Hydrothermal synthesis and solid-state structures of polynuclear technetium iodide compounds

A Decade of Dinuclear Technetium Complexes with Multiple Metal–Metal Bonds

Group 7 Metal–Metal Bonds

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