Boron-Substituted <i>o</i>-Carboranetrithiol To Construct Trimeric Cobalt Clusters

Zhang, Xiaolei; Tang, Xiao Yan; Yang, Jiajia; Li, Yi‐Zhi; Yan, Hong; Bregadze, V. I.

doi:10.1021/om400097m

Cited by 22 publications

(6 citation statements)

References 60 publications

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“…Herein, we report the synthesis and X-ray single-crystal structure of an achiral bidentate thiolate ligand (9,12-dimercapto-1,2- closo -carborane, C 2 B 10 H 10 S 2 H 2 with B–S bonds) protected nanocluster Ag 33 (C 2 B 10 H 10 S 2 ) 12 (abbreviated as Ag 13 @Ag 20 ) that crystallizes in the trigonal R 3̅ space group (No. 148).…”

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confidence: 99%

Symmetry Breaking of Atomically Precise Fullerene-like Metal Nanoclusters

Huang

Dong

et al. 2021

J. Am. Chem. Soc.

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Here we report a neutral fullerene-like core−shell homosilver Ag 13 @Ag 20 nanocluster that is fully protected by an achiral bidentate thiolate ligand (9,12-dimercapto-1,2-closo-carborane, C 2 B 10 H 10 S 2 H 2 ), which crystallizes in centrosymmetric space group R3̅ . Continuous Cu doping in the dodecahedral shell first induced symmetry breaking to generate chiral Ag 13 @Ag 20-n Cu n (6 ≥ n ≥ 2) containing two acetonitrile ligands in space group P2 1 2 1 2 1 , and then produced symmetric all-thiolated Ag 13 @Ag 20-n Cu n (20 ≥ n ≥ 13) in the higher space group Im3̅ . The selectively copper-doped Ag 13 @Ag 20-n Cu n (6 ≥ n ≥ 2) cluster has its structure reorganized to a lower symmetry that shows chiroptical activity. Moreover, structural distortion of Ag 13 @Ag 20-n Cu n (6 ≥ n ≥ 2) further expanded in chiral R-/S-propylene oxide, which induced a more prominent core-based CD response. This work revealed a novel mechanism of chirality generation at the atomic level through asymmetric shell-doping of metal nanoclusters, which provides new insight into the origin of chirality in inorganic nanostructures.

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confidence: 99%

Symmetry Breaking of Atomically Precise Fullerene-like Metal Nanoclusters

Huang

Dong

et al. 2021

J. Am. Chem. Soc.

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“…The reaction of boron-substituted dithiol 1 and Cp*Co(CO)I 2 [Cp* = pentamethylcyclopentadienyl] gave rise to the orange product 2 in excellent isolated yield (90%). Note that complex 2 is stable both in solution and in the solid state, in contrast to the similarly prepared CpCo(9,12-S 2 C 2 B 10 H 12 ), which is not stable enough in solution . The X-ray crystal structure of 2 (Figure ) validates the formation of a five-membered metallacycle ring CoS 2 B 2 , and the electron count confirms the 16 e cobalt center.…”

Section: Resultsmentioning

confidence: 80%

“…The analogous metal complexes (Ru, Os, Co, Rh, and Ir) containing 1,2-dicarba- closo -dodecaborane-1,2-dithiolate ligand have exhibited rich reaction chemistries − toward metal fragments, Lewis bases, alkynes, and others. However, similar dithiolato complexes based on the o -carborane-9,12-dithiolate ligand are still rare, and the synthesis of a boron-fused 1,4-dithiin has remained unknown to date. In this contribution, we first report the efficient route to boron-fused 1,4-dithiin compounds starting from the mononuclear 16 e half-sandwich cobalt complex containing an o -carborane-9,12-dithiolate.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Boron-Fused 1,4-Dithiin via Cobalt-Mediated Disulfuration of Alkyne at the o-Carborane-9,12-dithiolate Unit

2014

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We present the first synthesis and characterization of a series of boron-fused 1,4-dithiin compounds through the reactions of newly established boron-substituted 16e half-sandwich complex Cp*Co(9,12-S 2 C 2 B 10 H 10 ) with alkynes. The generated C 2 S 2 B 2 ring in these 1,4-dithiin species is a stable structural motif with electron-negative sulfur atoms, as evidenced by theoretical calculation and its solid-state self-assembly. Single-crystal X-ray analysis indicates that C carb −H•••S hydrogen bonding is involved in the self-assemblies of these compounds, which serves as a compatible interaction with stronger C carb −HAll new compounds are characterized by NMR, mass spectroscopy, and X-ray structural analysis.

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“…For instance, the nature of the R group in [Cu{S 2 P(OR) 2 }] n decides the nuclearity of the complex (R = Et, 39 n = 6; R = Pr i , 40 Recently a variety of bulky organochalcogen ligands have been employed for the synthesis of metal complexes. [43][44][45] We have employed 2-(4,6-dimethyl pyrimidyl)selenolate (I) for the synthesis of Cu(I), Ag(I) and Au(I) complexes. They have been characterized structurally while copper and silver complexes have been used as precursors for the synthesis of single phased metal chalcogenides.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, structures and DFT calculations of 2-(4,6-dimethyl pyrimidyl)selenolate complexes of Cu(i), Ag(i) and Au(i) and their conversion into metal selenide nanocrystals

et al. 2014

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The complexes [M{SeC4H(Me-4,6)2N2}]6 (M = Cu (1), Ag (2)) and [Au{SeC4H(Me-4,6)2N2}(PEt3)] (3) have been prepared and characterized by elemental analyses, UV-vis, NMR ((1)H, (13)C, (77)Se) spectroscopy and single crystal X-ray diffraction. The crystal structures of [Cu{SeC4H(Me-4,6)2N2}]6·H2O (1·H2O), [Ag{SeC4H(Me-4,6)2N2}]6·6MeOH·H2O (2·6MeOH·H2O) and [Au{SeC4H(Me-4,6)2N2}(PEt3)] (3) revealed that their metal centers acquire distorted square-pyramidal, trigonal and linear geometries, respectively. DFT calculations have been carried out to rationalize nuclearity in copper(i) chalcogenolate complexes. The calculations suggest that there is hardly any energy difference between the tetrameric and hexameric forms. Thermal behavior of [Cu{SeC4H(Me-4,6)2N2}]6 was studied by thermogravimetric analysis. Thermolysis of [M{SeC4H(Me-4,6)2N2}]6 (M = Cu, Ag) in 1-dodecanethiol (DDT) at 150 °C gave a cubic phase of Cu7Se4 and an orthorhombic phase of Ag2Se, respectively. Copper selenide (Cu7Se4) thin films were deposited on glass and silicon substrates by using [Cu{SeC4H(Me-4,6)2N2}]6 at 400 °C by AACVD.

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Boron-Substituted o-Carboranetrithiol To Construct Trimeric Cobalt Clusters

Cited by 22 publications

References 60 publications

Symmetry Breaking of Atomically Precise Fullerene-like Metal Nanoclusters

Symmetry Breaking of Atomically Precise Fullerene-like Metal Nanoclusters

Synthesis of Boron-Fused 1,4-Dithiin via Cobalt-Mediated Disulfuration of Alkyne at the o-Carborane-9,12-dithiolate Unit

Synthesis, structures and DFT calculations of 2-(4,6-dimethyl pyrimidyl)selenolate complexes of Cu(i), Ag(i) and Au(i) and their conversion into metal selenide nanocrystals

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