Some new types of quadruply bonded dirhenium compounds containing bridging carboxylato groups

Cotton, F. Albert; Gage, Larry D.; Rice, Catherine E.

doi:10.1021/ic50194a047

Cited by 22 publications

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References 2 publications

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“…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%

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

confidence: 99%