Bera, Jitendra K. ; Nethaji, Munirathnam ; Samuelson, Ashoka G. (1999) Synthesis and structures of oxyanion encapsulated copper(I)−dppm complexes (dppm = Bis (diphenylphosphino) methane) Inorganic Chemistry, 38 (8). pp. 1725-1735. ISSN 0020-1669
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Official URL: http://pubs.acs.org/doi/abs/10.1021/ic9801589?jour...
Related URL: http://dx.doi.org/10.1021/ic9801589
Abstract
Copper(I)-dppm complexes encapsulating the oxyanions ClO4-, NO3-, CH3C6H4CO2-, SO42-, and WO42- have been synthesized either by reduction of the corresponding Cu(II) salts and treatment with dppm, or by treating the complex [Cu2(dppm)2(dmcn)3](BF4)2 () (dmcn = dimethyl cyanamide) with the respective anion. The isolated complexes [Cu2(dppm)2(dmcn)2(ClO4)] (ClO4) (2), [Cu2(dppm)2(dmcn)2(NO3)] (NO3) (3), Cu2(dppm)2(NO3)2 (4), [Cu2(dppm)2(CH3C6H4CO2)2]dmcn•2THF (5), Cu2(dppm)2(SO4) (6), and [Cu3(dppm)3(Cl)(WO4)] 0.5H2O (7) have been characterized by IR, 1H and 31P{1H} NMR, UV−vis, and emission spectroscopy. The solid-state molecular structure of complexes 1, 2, 4, and 7 were determined by single-crystal X-ray diffraction. Pertinent crystal data are as follows: for 1, monoclinic P21/c, a = 11.376(10) Å, b = 42.503(7) Å, c = 13.530(6) Å, β = 108.08(2)°, V = 6219(3) Å3, Z = 4; for 2, monoclinic P21/n, a = 21.600(3) Å, b = 12.968(3) Å, c = 23.050(3) Å, β = 115.97(2)°, V = 5804(17) Å3, Z = 4; for 4, triclinic P1̄, a = 10.560(4) Å, b = 10.553(3) Å, c = 22.698(3) Å, α = 96.08(2)°, β = 96.03(2)°, γ = 108.31(2)°, V = 2362(12) Å3, Z = 2; and for 7, orthorhombic P212121, a = 14.407(4) Å, b = 20.573(7) Å, c = 24.176(6) Å, V = 7166(4) Å3, Z = 4. Analyses of the crystallographic and spectroscopic data of these complexes reveal the nature of interactions between the CuI−dppm core and oxyanion. The anchoring of the oxyanion to the Cun(dppm)n unit is primarily through coordination to the metal, but the noncovalent C−H•••O interactions between the methylene and phenyl protons of the dppm and oxygen atoms of the oxyanion play a significant role. The solid-state emission spectra for complexes 1−6 are very similar but different from 7. In CDCl3 solution, addition of ClO4- or NO3- (as their tetrabutylammonium salts) to 1 establishes a rapid equilibrium between the anion-complexed and uncomplexed forms. The association constant values for ClO4- and NO3- have been estimated from the 31P{1H} NMR spectra.
| Item Type: | Article |
|---|---|
| Source: | Copyright of this article belongs to American Chemical Society. |
| ID Code: | 99129 |
| Deposited On: | 20 Oct 2015 09:03 |
| Last Modified: | 20 Oct 2015 09:06 |
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