Self-Assembly of Reactive Linear Cu3 Building Blocks for Supramolecular Coordination Chemistry and Their Reactivity toward En Ligand Complexes
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- 作者：Martin Fleischmann ; Luis Dütsch ; Mehdi Elsayed Moussa ; Gábor Balázs ; Werner Kremer ; Christophe Lescop ; Manfred Scheer
- 刊名：Inorganic Chemistry
- 出版年：2016
- 出版时间：March 21, 2016
- 年：2016
- 卷：55
- 期：6
- 页码：2840-2854
- 全文大小：869K
- ISSN：1520-510X
文摘
This study describes the selective synthesis of linear, trinuclear, halide-bridged CuI 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 31P{1H} 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,η2:η2-E2)] (E = P (A1), As (A2)) led to unsymmetrically substituted [Cu3(μ-X)2(μ-dpmp)2(η1-L)]+ (4a–c: X = Cl–I, L = A1; 5: X = Cl, L = A2) complexes, reactions with the cyclo-P3 complex [CpMo(CO)2(η3-P3)] (B) afforded zigzag chain polymers [Cu3(μ-X)2(μ-dpmp)2(μ,η1:η1-B)]n[BF4]n (6a: X = Cl; 6b: X = Br) and symmetrically substituted complex [Cu3(μ-I)2(μ-dpmp)2(η1-B)2]+ (7). Reactions of 2a–c with cyclo-E5 complexes [Cp*Fe(η5-E5)] (E = P (C1), As (C2)) led to the isolation of one-dimensional coordination polymers [Cu3(μ-X)2(μ-dpmp)2(μ,η1:η1-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(η1-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{(η1-A1)}]+ (4a′) are presented.