Synthesis, Structures, and Properties of New Chalcogenide-Capped Octahedral Hexatechnetium(III) Complexes [Tc6S8X6]4- (X = Br, I), [Tc6Se8I2], and [Tc6Te15]

被引：6

作者：

Yoshimura, Takashi ^{[1
]}

Ikai, Takuya ^{[1
]}

Tooyama, Yuji ^{[1
]}

Takayama, Tsutomu ^{[2
]}

Sekine, Tsutomu ^{[3
]}

Kino, Yasushi ^{[4
]}

Kirishima, Akira ^{[5
]}

Sato, Nobuaki ^{[5
]}

Mitsugashira, Tioshiaki ^{[6
]}

Takahashi, Naruto ^{[1
]}

Shinohara, Atsushi ^{[1
]}

机构：

[1] Osaka Univ, Grad Sch Sci, Dept Chem, Osaka 5600043, Japan

[2] Daido Univ, Dept Chem, Aichi 4578530, Japan

[3] Tohoku Univ, Ctr Advancement Higher Educ, Sendai, Miyagi 9808576, Japan

[4] Tohoku Univ, Grad Sch Sci, Dept Chem, Sendai, Miyagi 9808576, Japan

[5] Tohoku Univ, Inst Multidisciplinary Res Adv Mat, Sendai, Miyagi 9808577, Japan

[6] Tohoku Univ, Inst Mat Res, Int Res Ctr Nucl Mat Sci, Oarai, Ibaraki 3111313, Japan

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2010年 / 08期

关键词：

Technetium; Chalcogens; Cluster compounds; Cyclic voltammetry; CLUSTER CHEMISTRY; DIMENSIONAL REDUCTION; CHALCOHALIDE CLUSTERS; POLYNUCLEAR CLUSTERS; MOLECULAR-STRUCTURE; CRYSTAL-STRUCTURES; REDOX PROPERTIES; HALIDE CLUSTERS; SOLID-STATE; TECHNETIUM;

D O I：

10.1002/ejic.200901057

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Chalcogenide-capped octahedral hexatechnetium(III) complexes, CS4[Tc6S8Br6]center dot CsBr (CS4[1]center dot CsBr) and (PPh4)(4)[Tc6S8Br6] {(PPh4)(4)[1]}, (PPh4)(4)[Tc6S8I6] {(PPh4)(4)[2]}, [Tc6Se8I2] ([3]), and [Tc6Te15] ([4]) were synthesized. Single-crystal X-ray structural studies were carried out for Cs-4[1]center dot CsBr, [3], and [4]. Sulfide-capped octahedral hexatechnetium(III) clusters [1](4-) and [2](4-) are discrete complex anions, whereas the selenide- and telluride-capped hexatechnetium(III) complexes adopt extended polymeric structures. A cyclic voltammogram of [1](4-) in CH3CN showed two one-electron redox waves: Tc-6(24e/23e) and Tc-6(23e/22e). The potential of the Tc-6(24e/23e) process is more positive than that of the Re-6(24e/23e) process for the hexarhenium analog [Re6S8X6](4-) (X = Br, I), whereas that of the TC6(23e/22e) process shifts to negative values compared to the potential of the Re6(23e/22e) process. Thus, the TC6(23e) mixed-valence state is thermodynamically less stable than Re-6(23e).

引用

页码：1214 / 1219

页数：6

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