[(TeMe2)Mn(CO)4(μ5-Te)(μ4-Te)Mn4(CO)12]−: ein fünffach koordinierender, verbrückender Telluridoligand in quadratisch-pyramidaler Geometrie

The reactions of appropriate ratios of K2TeO3 and [Mn2(CO)10)] in superheated methanol solutions lead to a series of novel cluster anions [Te4Mn3(CO)10] (1), [Te2Mn3(CO)9]2- (2), [Te2Mn3(CO)9]- (3), and [Te2Mn4(CO)12]2- (4). When cluster 1 is treated with [Mn2(CO)10]/KOH in methanol, paramagnetic cluster 2 is formed in moderate yield. Cluster 2 is oxidized by [Cu(MeCN)4]BF4 to give the closo-cluster [Te2Mn3(CO)9]- (3), while treatment of 2 with [Mn2(CO)10]/KOH affords the closo-cluster 4. IR spectroscopy showed that cluster 1 reacted with [Mn2(CO)10] to give cluster 4 via cluster 2. Clusters 1-4 were structurally characterized by spectroscopic methods or/and X-ray analyses. The core structure of 1 can be described as two [Mn(CO)3] groups doubly bridged by two Te2 fragments in a mu2-eta2 fashion. Both [Mn(CO)3] groups are further coordinated to one [Mn(CO)4] moiety. Cluster 2 is a 49 e- species with a square-pyramidal core geometry. While cluster 3 displays a trigonal-bipyramidal metal core, cluster 4 possesses an octahedral core geometry.

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Tellurium-Bridged Manganese Carbonyl Clusters: Synthesis and Structural Transformations of [Te4Mn3(CO)10]−, [Te2Mn3(CO)9]2−, [Te2Mn3(CO)9]−, and [Te2Mn4(CO)12]2−

Shieh

Chen

Yang

et al. 2001

Chem. Eur. J.

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Trigonal‐Bipyramidal and Square‐Pyramidal ChromiumManganese Chalcogenide Clusters, [E₂CrMn₂(CO)_n]²⁻ (E=S, Se, Te; n=9, 10): Synthesis, Electrochemistry, UV/Vis Absorption, and Computational Studies

Shieh

Chu

et al. 2013

Chemistry An Asian Journal

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The reactions of E powder (E=S, Se) with a mixture of Cr(CO)6 and Mn2(CO)10 in concentrated solutions of KOH/MeOH produced two new mixed Cr-Mn-carbonyl clusters, [E2CrMn2(CO)9](2-) (E=S, 1; Se, 2). Clusters 1 and 2 were isostructural with one another and each displayed a trigonal-bipyramidal structure, with the CrMn2 triangle axially capped by two μ3-E atoms. The analogous telluride cluster, [Te2CrMn2(CO)9](2-) (3), was obtained from the ring-closure of Te2Mn2 ring complex [Te2Mn2Cr2(CO)18](2-) (4). Upon bubbling with CO, clusters 2 and 3 were readily converted into square-pyramidal clusters, [E2CrMn2(CO)10](2-) (E=Se, 5; Te, 6), accompanied with the cleavage of one Cr-Mn bond. According to SQUID analysis, cluster 6 was paramagnetic, with S=1 at room temperature; however, the Se analogue (5) was spectroscopically proposed to be diamagnetic, as verified by TD-DFT calculations. Cluster 6 could be further carbonylated, with cleavage of the Mn-Mn bond to produce a new arachno-cluster, [Te2CrMn2(CO)11](2-) (7). The formation and structural isomers, as well as electrochemistry and UV/Vis absorption, of these clusters were also elucidated by DFT calculations.

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Copper Halide‐Bridged Ruthenium Telluride Carbonyl Complexes: Discovery of the Semiconducting Cluster Chain Polymer {[PPh₄]₂[Te₂Ru₄(CO)₁₀Cu₄Br₂Cl₂]⋅THF}_∞

Shieh

Hsu

Sheu

et al. 2007

Chemistry A European J

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A new series of Te-Ru-Cu carbonyl complexes was prepared by the reaction of K(2)TeO(3) with [Ru(3)(CO)(12)] in MeOH followed by treatment with PPh(4)X (X=Br, Cl) and [Cu(MeCN)(4)]BF(4) or CuX (X=Br, Cl) in MeCN. When the reaction mixture of K(2)TeO(3) and [Ru(3)(CO)(12)] was first treated with PPh(4)X followed by the addition of [Cu(MeCN)(4)]BF(4), doubly CuX-bridged Te(2)Ru(4)-based octahedral clusters [PPh(4)](2)[Te(2)Ru(4)(CO)(10)Cu(2)X(2)] (X=Br, [PPh(4)](2)[1]; X=Cl, [PPh(4)](2)[2]) were obtained. When the reaction mixture of K(2)TeO(3) and [Ru(3)(CO)(12)] was treated with PPh(4)X (X=Br, Cl) followed by the addition of CuX (X=Br, Cl), three different types of CuX-bridged Te-Ru carbonyl clusters were obtained. While the addition of PPh(4)Br or PPh(4)Cl followed by CuBr produced the doubly CuBr-bridged cluster 1, the addition of PPh(4)Cl followed by CuCl led to the formation of the Cu(4)Cl(2)-bridged bis-TeRu(5)-based octahedral cluster compound [PPh(4)](2)[{TeRu(5)(CO)(14)}(2)Cu(4)Cl(2)] ([PPh(4)](2)[3]). On the other hand, when the reaction mixture of K(2)TeO(3) and [Ru(3)(CO)(12)] was treated with PPh(4)Br followed by the addition of CuCl, the Cu(Br)CuCl-bridged Te(2)Ru(4)-based octahedral cluster chain polymer {[PPh(4)](2)(Te(2)Ru(4)(CO)(10)Cu(4)Br(2)Cl(2)).THF}(infinity) ({[PPh(4)](2)[4].THF}(infinity)) was produced. The chain polymer {[PPh(4)](2)[4].THF}(infinity) is the first ternary Te-Ru-Cu cluster and shows semiconducting behavior with a small energy gap of about 0.37 eV. It can be rationalized as resulting from aggregation of doubly CuX-bridged clusters 1 and 2 with two equivalents of CuCl or CuBr, respectively. The nature of clusters 1-4 and the formation and semiconducting properties of the polymer of 4 were further examined by molecular orbital calculations at the B3LYP level of density functional theory.

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[(TeMe2)Mn(CO)4(μ5-Te)(μ4-Te)Mn4(CO)12]−: ein fünffach koordinierender, verbrückender Telluridoligand in quadratisch-pyramidaler Geometrie

Cited by 7 publications

References 47 publications

Tellurium-Bridged Manganese Carbonyl Clusters: Synthesis and Structural Transformations of [Te4Mn3(CO)10]−, [Te2Mn3(CO)9]2−, [Te2Mn3(CO)9]−, and [Te2Mn4(CO)12]2−

Tellurium-Bridged Manganese Carbonyl Clusters: Synthesis and Structural Transformations of [Te4Mn3(CO)10]−, [Te2Mn3(CO)9]2−, [Te2Mn3(CO)9]−, and [Te2Mn4(CO)12]2−

Trigonal‐Bipyramidal and Square‐Pyramidal ChromiumManganese Chalcogenide Clusters, [E₂CrMn₂(CO)_n]²⁻ (E=S, Se, Te; n=9, 10): Synthesis, Electrochemistry, UV/Vis Absorption, and Computational Studies

Copper Halide‐Bridged Ruthenium Telluride Carbonyl Complexes: Discovery of the Semiconducting Cluster Chain Polymer {[PPh₄]₂[Te₂Ru₄(CO)₁₀Cu₄Br₂Cl₂]⋅THF}_∞

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[(TeMe2)Mn(CO)4(μ5-Te)(μ4-Te)Mn4(CO)12]−: ein fünffach koordinierender, verbrückender Telluridoligand in quadratisch-pyramidaler Geometrie

Cited by 7 publications

References 47 publications

Tellurium-Bridged Manganese Carbonyl Clusters: Synthesis and Structural Transformations of [Te4Mn3(CO)10]−, [Te2Mn3(CO)9]2−, [Te2Mn3(CO)9]−, and [Te2Mn4(CO)12]2−

Tellurium-Bridged Manganese Carbonyl Clusters: Synthesis and Structural Transformations of [Te4Mn3(CO)10]−, [Te2Mn3(CO)9]2−, [Te2Mn3(CO)9]−, and [Te2Mn4(CO)12]2−

Trigonal‐Bipyramidal and Square‐Pyramidal ChromiumManganese Chalcogenide Clusters, [E2CrMn2(CO)n]2− (E=S, Se, Te; n=9, 10): Synthesis, Electrochemistry, UV/Vis Absorption, and Computational Studies

Copper Halide‐Bridged Ruthenium Telluride Carbonyl Complexes: Discovery of the Semiconducting Cluster Chain Polymer {[PPh4]2[Te2Ru4(CO)10Cu4Br2Cl2]⋅THF}∞

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Trigonal‐Bipyramidal and Square‐Pyramidal ChromiumManganese Chalcogenide Clusters, [E₂CrMn₂(CO)_n]²⁻ (E=S, Se, Te; n=9, 10): Synthesis, Electrochemistry, UV/Vis Absorption, and Computational Studies

Copper Halide‐Bridged Ruthenium Telluride Carbonyl Complexes: Discovery of the Semiconducting Cluster Chain Polymer {[PPh₄]₂[Te₂Ru₄(CO)₁₀Cu₄Br₂Cl₂]⋅THF}_∞