LCu(μ-X)2CuL compounds: An induced cuprophilic interaction.
In: Polyhedron, Jg. 116 (2016-09-25), S. 204-215
academicJournal
Zugriff:
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 dinuclear compounds, 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 ( β ) 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. Five PMe 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 2 p 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. [ABSTRACT FROM AUTHOR]
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LCu(μ-X)2CuL compounds: An induced cuprophilic interaction.
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Autor/in / Beteiligte Person: | Chen, Peter E. ; McNeely, James ; Lum, June S. ; Gardner, Evan J. ; Phillips, Val ; Golen, James A. ; Rheingold, Arnold L. ; Doerrer, Linda H. |
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Zeitschrift: | Polyhedron, Jg. 116 (2016-09-25), S. 204-215 |
Veröffentlichung: | 2016 |
Medientyp: | academicJournal |
ISSN: | 0277-5387 (print) |
DOI: | 10.1016/j.poly.2016.05.033 |
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