Bera, Jitendra K. ; Nethaji, Munirathnam ; Samuelson, Ashoka G. (1998) Anion-controlled nuclearity and metal−metal distances in copper(I)−dppm complexes (dppm = Bis(diphenylphosphino)methane) Inorganic Chemistry, 38 (2). pp. 218-228. ISSN 0020-1669
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Official URL: http://pubs.acs.org/doi/abs/10.1021/ic980515f?jour...
Related URL: http://dx.doi.org/10.1021/ic980515f
Abstract
Dicapped triangular copper(I)−dppm complexes Cu3(dppm)3(μ3-X)2+ (X = Cl, Br, and I) and monocapped Cu3(dppm)3(μ3-OH)2+ have been prepared by treating the dimeric Cu2(dppm)2(CH3CN)4(ClO4)2 or Cu2(dppm)2(dmcn)3(BF4)2 (dmcn = dimethylcyanamide) complexes with the corresponding bridging ligand X-. The trimeric complexes Cu3(dppm)3(μ3-OH)(BF4)2 and Cu3(dppm)3(μ3-Cl)2Cl can be converted to dimers Cu2(dppm)2(dmcn)3(BF4)2 and Cu2(dppm)2(dmcn)(Cl)2 by reaction with HBF4, dmcn, and excess dmcn, respectively. The complexes synthesized by the above means, Cu3(dppm)3(μ3-Cl)2ClO4 (1>), Cu3(dppm)3(μ3-Br)2ClO4 (2)•2THF, Cu3(dppm)3(μ3-I)2I• 2CH2Cl2•CH3OH (3), and Cu2(dppm)2(dmcn)(Cl)2•2dmcn (4) have been characterized by IR, 1H and 31P{1H} NMR, and solid-state emission spectroscopy. The solid-state molecular structures of complexes 2, b3, and 4 were determined from single-crystal X-ray diffraction studies. Apart from confirming the nuclearity, the structural information reveals interesting variations in the Cu•••Cu distances in dimeric and trimeric complexes. A simple geometric correlation between the Cu−X and Cu•••Cu distances is noted in the trimeric complexes with an important exception of the dicapped Cl complex. Ab initio electronic structure calculations of the homo dicapped Cu3X2+ (X= Cl, Br, HO, and HC2) and mixed-capped Cu3XY+ (X = Cl, Y = HC2) species have been carried out at the MP2 level of theory using valence-DZP-quality basis sets with effective core potentials on copper. The computed Cu•••Cu distances reproduce the observed experimental trend. Analyses of the electronic structures of the optimized model Cu3X2+ complexes reveal the electronic tuning of Cu•••Cu distances by the capping ligand. The variation of Cu•••Cu distances in monobridged dimeric copper(I)−dppm complexes can also be rationalized along similar lines.
| Item Type: | Article |
|---|---|
| Source: | Copyright of this article belongs to American Chemical Society. |
| ID Code: | 99128 |
| Deposited On: | 20 Oct 2015 09:09 |
| Last Modified: | 20 Oct 2015 09:09 |
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