192629-65-5Relevant academic research and scientific papers
Binuclear copper(I) complexes containing bis(diphenylphosphino)methane bridging ligands. X-ray crystal structure of [Cu2(dppm)2(Py)2(NO3)](NO 3) CH3OH
Ruina, Yang,Kunhua, Lin,Yimin, Hou,Dongmei, Wang,Douman, Jin
, p. 4033 - 4038 (1997)
Binuclear copper(I) complexes [Cu(dppm)(phen)]2(NO3)2 (1), dppm = Ph2PCH2PPh2, [Cu(dppm)(2,2′-bipy)]2(NO3)2(2), [Cu2(dppm)2(C7/s
Synthesis and structures of oxyanion encapsulated copper(I)-dppm complexes (dppm = bis(diphenylphosphino)methane)
Bera, Jitendra K.,Nethaji, Munirathnam,Samuelson, Ashoka G.
, p. 1725 - 1735 (2008/10/08)
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 (1) (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(CH3C6H 4CO2)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) A?, b = 42.503(7) A?, c = 13.530(6) A?, β= 108.08(2)°, V = 6219(3) A?3, Z = 4; for 2, monoclinic P21/n, a = 21.600(3) A?, b = 12.968(3) A?, c = 23.050(3) A?, β= 115.97(2)°, V = 5804(17) A?3, Z = 4; for 4, triclinic P1?, a = 10.560(4) A?, b = 10.553(3) A?, c = 22.698(3) A?, α = 96.08(2)°, β= 96.03(2)°, γ = 108.31(2)°,V= 2362(12) A?3, Z = 2; and for 7, orthorhombic P212121, a = 14.407(4) A?, b = 20.573(7) A?, c = 24.176(6) A?, V = 7166(4) A?3, Z = 4. Analyses of the crystallographic and spectroscopic data of these complexes reveal the nature of interactions between the Cu1-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.
