Synthesis and characterization of {[CuI3Sn2(OBut)6]+[CuII(hfac)3]−} – A heterometallic cluster with unique triangular copper(I) core

Lieberman, Craig M.; Vreshch, Volodimir D.; Filatov, Alexander S.; Dikarev, Evgeny V.

doi:10.1016/j.ica.2014.08.045

Cited by 6 publications

(7 citation statements)

References 76 publications

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“…The obtained bimetallic complexes consisted of two homoleptic tris-β-diketonate fragments forming an ion pair (Figure 23). Copper(II) β-diketonate reacted with tin(II) alkoxide to give the six-nuclear [Sn-Cu] complex (47) (Scheme 18) [92]. Similarly to bimetallic [Sn-M] complexes 44-46, an ion pair was formed as a result of the redox reaction.…”

Section: Heteronuclear Complexes With Isolated Metal Centersmentioning

confidence: 99%

“…Copper(II) tris-β-diketonate represented the anionic part, while the oxygen atoms of tin(II) alkoxides were coordinated to copper(I) ions in the cationic part (Figure 24). Copper(II) β-diketonate reacted with tin(II) alkoxide to give the six-nuclear [Sn-Cu] complex (47) (Scheme 18) [92]. Similarly to bimetallic [Sn-M] complexes 44-46, an ion pair was formed as a result of the redox reaction.…”

Section: Heteronuclear Complexes With Isolated Metal Centersmentioning

confidence: 99%

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Heterometallic Molecular Architectures Based on Fluorinated β-Diketone Ligands

et al. 2022

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This review summarizes the data on the synthesis of coordination compounds containing two or more different metal ions based on fluorinated β-diketonates. Heterometallic systems are of high interest in terms of their potential use in catalysis, medicine and diagnostics, as well as in the development of effective sensor devices and functional materials. Having a rich history in coordination chemistry, fluorinated β-diketones are well-known ligands generating a wide variety of heterometallic complexes. In this context, we focused on both the synthetic approaches to β-dicarbonyl ligands with additional coordination centers and their possible transformations in complexation reactions. The review describes bi- and polynuclear structures in which β-diketones are the key building blocks in the formation of a heterometallic framework, including the examples of both homo- and heteroleptic complexes.

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Section: Heteronuclear Complexes With Isolated Metal Centersmentioning

confidence: 99%

Section: Heteronuclear Complexes With Isolated Metal Centersmentioning

confidence: 99%

Heterometallic Molecular Architectures Based on Fluorinated β-Diketone Ligands

et al. 2022

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“…Further studies involving both perfluorinated alkoxides and copper have demonstrated their ability to obtain heterometallic complexes containing both Cu and Ba (Purdy & George 1991;Borup et al, 1997) and in the use of such compounds in the oxycupration of tetrafluoroethylene (Ohashi et al, 2017). Of particular interest are the alkoxide complexes of copper(I), which often form cluster compounds (Purdy & George 1995;Borup et al, 1997;Purdy & George 1998;Anson et al, 2005;Lieberman et al, 2015). Within this set of compounds, there are those that form tetra-Cu I squares bridged along the edges by oxygen donors (Greiser & Weiss, 1976;McGeary et al, 1992;Terry et al, 1996;Lopes et al, 1997;Nikitinsky et al, 2000;Hå kansson et al, 2000;Krossing, 2012;Bellow et al, 2015).…”

Section: Chemical Contextmentioning

confidence: 99%

Tetrakis[μ₂-1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-olato]tetrakis(μ₃-2-methylpropan-2-olato)octacopper(I)

Purdy

Butcher

2021

Acta Cryst E

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The title compound, [Cu8(C4H9O)4(C4F9O)4], crystallizes in the monoclinic space group, P21/n and contains a self-assembly of two C16H18Cu4F18O4 units linked by bridging tert-butyl groups [Cu—O bonds of length 2.3779 (15) and 2.4248 (15) Å], generating a centrosymmetric dimer. The asymmetrical unit, C16H18Cu4F18O4, contains an almost square-planar arrangement of the four Cu atoms linked by bridging tert-butyl and perfluorinated tert-butyl groups with Cu—Cu distances ranging from 2.7108 (4) to 2.7612 (4) Å and Cu —Cu—Cu angle values close to 90° [ranging from 89.459 (10)° to 90.025 (11)°]. These dimers are further linked by weak C—H...F and F...F interactions. As is commonly encountered in perfluorinated tert-butyl groups, one of the CF3 groups is disordered and was refined with two equivalent conformations with occupancies of 0.74 (3) and 0.26 (3).

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“…Other cuprophilic interactions have also been observed that result from structurally imposed interactions including with NHC ligands, 10,11 bridging alkoxide 12 and siloxides 13 poly-pyridyl groups, 14 germylene dioxide, 15 amidinate, 16 carboxylate, 17 formamidinate, 18 bridging perthiocarboxylate, 19 cyanuric acid, 20 or binucleatingpyridyl-imine ligands, 21 as well as mechanical compression, 22,23 or just sterically unencumbered Cu(I) centers in clusters, 24 and other circumstances. [25][26][27][28][29] Alvarez's Framework Electron Count (FEC) is a simple molecular orbital approach to understanding the extent of metal-metal interaction in [M 2 X 2 ] rings.…”

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confidence: 99%

“…[33][34][35] In addition to orbital overlap, substituent steric properties and metal-center electronic character are also important factors in determining the extent of cuprophilic interactions. 12,13 For copper(I) dimers with a [Cu 2 X 2 ] core, the FEC model does not predict any cuprophilic interaction, because the four Cu-X bonds give an FEC of eight.…”

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confidence: 99%

LCu(μ-X)2CuL compounds: An induced cuprophilic interaction

et al. 2016

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A trio of dimeric copper(I) complexes of the formula [(Ph 3 P)Cu(μ-X) 2 Cu(PPh 3)] (X = OC 6 F 5 , 1, OC 4 F 9 , 2, OCPh(CF 3) 2 , 3) were prepared and characterized by X-ray crystallography, elemental analysis, and NMR spectroscopy (1 H, 13 C, 19 F, 31 P), as was the monomeric [(cy 3 P)Cu(OC 4 F 9)] (cy = cyclohexyl,4). Solution conductivity studies demonstrate that all three new dinuclearcompounds, as well as the known [(Ph 3 P)Cu(μ-OC 4 H 9) 2 Cu(PPh 3)], 2-H, are neutral species in solution and do not rearrange into ion pairs. The fold angle () varies among these four dimers and the Cu(I) … Cu(I) distance in the structure of 2, 2.8315(5) Å, is cuprophilic. The Cu(I) … Cu(I) distances for 1, 2-H, and 3 are 3.0533(5), 2.890(2), and 3.0169(6) Å respectively.Density functional theory (DFT) calculations were performed on 1, 2, 3, and 2-H, as well as the hypothetical 1-H, and several related models. FivePMe 3 models, 1(Me), 1-H(Me), 2(Me), 2-H(Me), and 3(Me) were also studied as well as five monomers [(Me 3 P)CuX]1-mon, 1-H(mon), 2-mon, 2-H(mon), and 3-mon to understand the electronic reasons for folding in this group of compounds. A Natural Energy Decomposition Analysis (NEDA) indicates that electrostatic stabilizations are the dominant factor governing the strength of interaction between monomeric fragments in 1(Me)-3(Me). NBO analysis reveals that 1(Me) and 1-H(Me) do not display any cuprophilic interactions. The folding angle observed in 2(Me), 2-H(Me), and 3(Me), which is correlated with an increased delocalization from the oxygen 2p z lone pairs, brings the metal centers into sufficient propinquity to have weak Cu … Cu orbital interactions. Weak luminescence behavior at room-temperature is also consistent with these assignments.

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Synthesis and characterization of {[CuI3Sn2(OBut)6]+[CuII(hfac)3]−} – A heterometallic cluster with unique triangular copper(I) core

Cited by 6 publications

References 76 publications

Heterometallic Molecular Architectures Based on Fluorinated β-Diketone Ligands

Heterometallic Molecular Architectures Based on Fluorinated β-Diketone Ligands

Tetrakis[μ₂-1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-olato]tetrakis(μ₃-2-methylpropan-2-olato)octacopper(I)

LCu(μ-X)2CuL compounds: An induced cuprophilic interaction

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Synthesis and characterization of {[CuI3Sn2(OBut)6]+[CuII(hfac)3]−} – A heterometallic cluster with unique triangular copper(I) core

Cited by 6 publications

References 76 publications

Heterometallic Molecular Architectures Based on Fluorinated β-Diketone Ligands

Heterometallic Molecular Architectures Based on Fluorinated β-Diketone Ligands

Tetrakis[μ2-1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-olato]tetrakis(μ3-2-methylpropan-2-olato)octacopper(I)

LCu(μ-X)2CuL compounds: An induced cuprophilic interaction

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Tetrakis[μ₂-1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-olato]tetrakis(μ₃-2-methylpropan-2-olato)octacopper(I)