Mesitylcopper:  Tetrameric and Pentameric

Eriksson, Henrik; Håkansson, Mikael

doi:10.1021/om970462u

Cited by 114 publications

(93 citation statements)

References 17 publications

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“…The plane of the bridging aryl ligands are characteristically orientated perpendicular to the Cu 4 plane. In some cases [14,15,17] the C ipso atoms lie in the same plane as the Cu 4 core, but in the other examples [13,16,18] they are located alternately above and below the Cu 4 plane forming a puckered ring as in Figure 2 (top). The pinching in of the Cu atoms shown in Figure 1 varies considerably with some C-Cu-C units [13,16] being linear within experimental error.…”

Section: A C H T U N G T R E N N U N G (Cctbu) 4 ] (2) [Cu 12 -A C Hmentioning

confidence: 99%

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Copper(I) Alkynyl Clusters, [Cu_x+y(hfac)_x(CCR)_y], with Cu₁₀–Cu₁₂ Cores

Baxter

Higgs

Bailey

et al. 2006

Chemistry A European J

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The facile syntheses and the structures of five new Cu(I) alkynyl clusters, [Cu(12)(hfac)(8)(C[triple chemical bond]CnPr)(4)(thf)(6)]xTHF (1), [Cu(12)(hfac)(8)(C[triple chemical bond]CtBu)(4)] (2), [Cu(12)(hfac)(8)(C[triple chemical bond]CSiMe(3))(4)] (3), [Cu(10)(hfac)(6)(C[triple chemical bond]CtBu)(4)(diethyl ether)]/[Cu(10)(hfac)(6)(C[triple chemical bond]CtBu)(3)(C[triple chemical bond]CnPr)(diethyl ether)] (4) and [Cu(10)(hfac)(6)(C[triple chemical bond]CtBu)(4)(diethyl ether)] (5) are reported, in which hfacH=1,1,1,5,5,5-hexafluoropentan-2,4-dione. The first independent molecule found in the crystals of 4 (4 a) proved to be chemically identical to 5. The Cu(10) and Cu(12) cores in these clusters are based on a central "square" Cu(4)C(4) unit. Whilst the connectivities of the Cu(10) or Cu(12) units remain identical the geometries vary considerably and depend on the bulk of the alkynyl group, weak coordination of ether molecules to copper atoms in the core and CuO intramolecular contacts formed between Cu-hfac units on the periphery of the cluster. Similar intermolecular contacts and interlocking of Cu-hfac units are formed in the simple model complex [Cu(2)(hfac)(2)(HC[triple chemical bond]CtBu)] (6). When linear alkynes, C(n)H(2n+1)C[triple chemical bond]CH, are used in the synthesis and non-coordinating solvents are used in the workup, further association of the Cu(4)C(4) cores occurs and clusters with more than eighteen copper atoms are isolated.

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Section: A C H T U N G T R E N N U N G (Cctbu) 4 ] (2) [Cu 12 -A C Hmentioning

confidence: 99%

“…Subsequently [Cu 4 A C H T U N G T R E N N U N G (aryl) 4 ] analogues have been characterized [aryl = 2,4,6-triisopropylphenyl (2,4,6-iPr 3 C 6 H 2 À ), [13] pentamethylphenyl (C 6 Me 5 À ), [14] thienyl (C 4 H 3 S À ), [15] pentafluorophenyl (C 6 F 5 À ), [16] mesityl (2,4,6-Me 3 C 6 H 2 À ) [17] and o-…”

Section: Introductionmentioning

confidence: 99%

Copper(I) Alkynyl Clusters, [Cu_x+y(hfac)_x(CCR)_y], with Cu₁₀–Cu₁₂ Cores

Baxter

Higgs

Bailey

et al. 2006

Chemistry A European J

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“…The choice of the copper(I) hydrides was based on the well known tendency of copper(I) centers to cluster together in a variety of organocopper(I) compounds involving even the alkyl groups as bridging ligands, a representative example being the cyclic Cu 4 R 4 tetramer [2][3][4][5][6][7][8][9][10][11]. The cyclic hydrocoppers(I) and some of their substituted derivatives were predicted to be stable species with a perfectly planar configuration, thus expanding the borders of inorganic chemistry into the realm of organic chemistry by building molecules containing bonds that are characterized by a common ring-shaped electron density, more commonly seen in organic molecules, with new properties and chemical reactivity.…”

Section: Introductionmentioning

confidence: 99%

How the Aromatic 4-Membered Hydrido-Bridged Copper Rings Respond to Successive Nucleophilic Attack?

Tsipis¹,

Charistos²

2008

TOMEJ

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Electronic structure calculations (B3LYP/6-311+G**) predict that nucleophilic attack of the aromatic cycloCu 4 (μ-) 4 ring yields ligand-stabilized tetranuclear Cu 4 clusters formulated as cyclo-Cu 4 (μ-) 4 Nuc n (n = 1-4; Nuc = N 2 , CO, H 2 O, NH 3 and PH 3 ). Depending on the number of added nucleophiles, the tetranuclear Cu 4 clusters adopt planar, bent or 3D tetrahedral geometries. These molecules exhibit aromatic character, which is primarily due to 4s and 3d cyclic electron delocalization over the Cu 4 framework (s and d-orbital aromaticity). The aromaticity of the novel ligand stabilized tetranuclear Cu 4 clusters was verified by a number of established criteria of aromaticity. In particular, the nucleusindependent chemical shift, NICS(0) and NICS(1) and their out-of-plane components NICS zz (0), NICS zz (1) and the NICS scan pictures are indicative for the aromaticity of the planar, bent and tetrahedral Cu 4 clusters. The effect of the substituents on the aromatic character of the Cu 4 clusters is also a main concern of the present work. It was found that increasing the number of the attacking nucleophiles increases the diatropic response of the aromatic tetranuclear Cu 4 clusters. Moreover, the aromaticity of the 3D structures (spherical aromaticity) is higher than the aromaticity of the planar and bent structures. The effect of the coordinated nucleophiles, Nuc, on the stability, geometry, electronic structure and bonding mode of the cyclo-Cu 4 (μ-) 4 Nuc n molecules is also thoroughly discussed.

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“…28 Hence, in order to allow comparisons to be drawn with the novel and are also typical for 2e−3c bonding of an aryl group to two copper atoms. [29][30][31] There is no evidence for Cu-C interactions between the tetrameric rings in 1, the shortest Cu…C inter- …”

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confidence: 99%