Structural, Far-IR, and Solid State 31P NMR Studies of Two-Coordinate Complexes of Tris(2,4,6-trimethoxyphenyl)phosphine with Copper(I) Iodide
| Autor: | Graham A. Bowmaker, Lisa-Jane Baker, Peter Conrad Healy, Robert D. Hart, Allan H. White, Peta J. Harvey |
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| Rok vydání: | 1994 |
| Předmět: | |
| Zdroj: | Inorganic Chemistry. 33:3925-3931 |
| ISSN: | 1520-510X 0020-1669 |
| Popis: | Reaction of the highly basic, sterically hindered tertiary phosphine ligand tris(2,4,6-trimethoxyphenyl)phosphine (TMPP) with copper(I) iodide in acetonitrile yields 1:1 complexes whose structures depend on the mole ratio of the reactants. The crystals which first deposit from the reaction of TMPP with Cul in a 1:2 ratio are the 1:1 molecular adduct [(TMPP)CuI], whose structure was determined by room-temperature single-crystal X-ray studies. This complex is isomorphous with the corresponding Cl and Br compounds and their Ag analogues, crystallizing in the tetragonal space group P4, with a = 15.292(7) A, c = 12.748(5) A, Z = 4, and R = 0.044 for N = 2027 “observed” (I> 3σ(I)) reflections. The complex contains mononuclear [(TMPP)CuI] molecules with approximately linear two-coordination about the copper atom; Cu–P = 2.188(4) A, CuI = 2.417(2) A, P–Cu–I = 171.0(1)°. The slight deviation from linearity presumably arises because of contacts with the methoxy oxygen atoms; the Cu-O contacts involving the nearest ortho-methoxy oxygen atoms on the three phenyl groups in the ligand are 3.07(1), 2.858(7), and 2.674(9) A. This represents the first structural characterization of a compound with a two-coordinate P-CuI grouping, and the first example of a two-coordinate complex of CuI with a neutral ligand. The far-infrared spectrum shows a v(CuI) band at 239 cm. Reaction of TMPP with Cul in a 1:1 mole ratio in acetonitrile yields a different product of 1:1 stoichiometry which is shown by means of solid state P NMR and IR spectroscopy to be an ionic complex of the type [(TMPP)Cu][CuI]. |
| Databáze: | OpenAIRE |
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