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Self-Assembly of Reactive Linear Cu3 Building Blocks for Supramolecular Coordination Chemistry and Their Reactivity toward En Ligand Complexes

Abstract : This study describes the selective synthesis of linear, trinuclear, halide-bridged Cu(I) complexes [Cu3(μ-X)2(μ-dpmp)2(MeCN)2](+) (1a: X = Cl; 1b: X = Br; 1c: X = I) stabilized by the tridentate dpmp ligand obtained by self-assembly reactions in THF/MeCN. Upon drying, the MeCN ligands can be removed and the complexes are transformed to the reactive parent trinuclear [Cu3(μ-X)2(μ-dpmp)2](+) (2a-c) building blocks with two vacant coordination sites on the terminal Cu atoms. Another synthesis in CH2Cl2 directly yields 2a-c. Additionally, two related isomeric compounds, 2a* and 2c*, and two CH2Cl2-ligated complexes, [Cu3(μ-X)2(μ-dpmp)2(CH2Cl2)2](+) (X = Br (3b), I (3c)), were structurally characterized. The frameworks of the cationic [Cu3(μ-X)2(μ-dpmp)2](+) complexes are stable in solution at low temperatures and show dynamic coordination behavior at elevated temperatures, indicated by new signals arising in the (31)P\(1)H\ NMR spectra. This evolution cannot be shifted back by decreasing the temperature again. However, cationic [Cu3(μ-X)2(μ-dpmp)2](+) (X = Cl, Br, I) complexes can be obtained selectively in the solid state upon crystallization. Although reactions of 2a-c with complexes [\CpMo(CO)2\2(μ,η(2):η(2)-E2)] (E = P (A1), As (A2)) led to unsymmetrically substituted [Cu3(μ-X)2(μ-dpmp)2(η(1)-L)](+) (4a-c: X = Cl-I, L = A1; 5: X = Cl, L = A2) complexes, reactions with the cyclo-P3 complex [CpMo(CO)2(η(3)-P3)] (B) afforded zigzag chain polymers [Cu3(μ-X)2(μ-dpmp)2(μ,η(1):η(1)-B)]n[BF4]n (6a: X = Cl; 6b: X = Br) and symmetrically substituted complex [Cu3(μ-I)2(μ-dpmp)2(η(1)-B)2](+) (7). Reactions of 2a-c with cyclo-E5 complexes [Cp*Fe(η(5)-E5)] (E = P (C1), As (C2)) led to the isolation of one-dimensional coordination polymers [Cu3(μ-X)2(μ-dpmp)2(μ,η(1):η(1)-L)]n[BF4]n (8a-b: X = Cl-Br, L = C1; 9: X = Cl, L = C2) and symmetrically substituted complex [Cu3(μ-I)2(μ-dpmp)2(η(1)-C1)2](+) (10). All products exhibit a trinuclear, cationic [Cu3(μ-X)2(μ-dpmp)2](+) complex as the central structural motif. Variation of the intramolecular Cu-Cu distances inside the Cu3 complexes is discussed, and supporting DFT computations for the model complex [Cu3(μ-Cl)2(dmmp)2\(η(1)-A1)\](+) (4a') are presented
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-01286282
Contributor : Nelly Brenner <>
Submitted on : Thursday, March 10, 2016 - 3:37:05 PM
Last modification on : Thursday, March 5, 2020 - 2:28:09 PM

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Martin Fleischmann, Luis Dütsch, Mehdi Elsayed Moussa, Gábor Balázs, Werner Kremer, et al.. Self-Assembly of Reactive Linear Cu3 Building Blocks for Supramolecular Coordination Chemistry and Their Reactivity toward En Ligand Complexes. Inorganic Chemistry, American Chemical Society, 2016, 55 (6), pp.2840-54. ⟨10.1021/acs.inorgchem.5b02641⟩. ⟨hal-01286282⟩

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