| 词条 | Symbiosis (chemical) |
| 释义 |
}} The biological term symbiosis was adopted for chemistry by Jørgensen in 1964,[1] who applied it to the process by which, say, a hard ligand on a metal predisposes the metal to receive another hard ligand rather than a soft ligand. In fact, two superficially antithetical phenomena occur: symbiosis and antisymbiosis. Chemical antisymbiosisThis is found principally with soft metals. Two soft ligands in mutual trans position will have a destabilizing effect on each other.[2] The effect is also found with borderline metals in the presence of high trans effect ligands. As illustration, the Selenocyanate ion trans to the soft carbon dioxide in trans-Rh(PPh3)2(CO)(NCSe) bonds via the Nitrogen, the harder of its two donors.[3] The phenomenon may be explained in terms of a trans influence: “With two π-acid ligands in mutual trans positions at a class-b metal, there would be a destabilizing competition for the dπ electrons on the metal. A π-acid bonded to a soft metal thus makes a metal a harder Lewis acid. Similarly a soft σ-donor will tend to polarize the electron density on a soft metal, causing it to favour an electrovalently bonded ligand in the trans position.”[4] Chemical symbiosisThis effect occurs with class-a metals such as Iron(II). The Cyclopentadienyl complex (C5H5)Fe(CO)2(SCN) is a typical example. The cyclopentadienyl directing the thiocyanate to bond through its softer Sulphur donor.[5] A more definitive example are the halopentamminocobalt(III) ions, Co(NH3)5X2+, which are more stable when the halogen, X, is Fluoride than with [Iodine], and the Halopentcyanocobalt(III) ions, Co(CN)5X3−, which are most stable when the halogen is [iodine].[6] “Hard bases (electronegative donor atoms) retain their valence (outer shell) electrons when attached to a given central metal ion, thus enabling the metal ion to retain more of its positive charge, making it a hard Lewis acid. With soft bases the central metal atom is made a softer Lewis acid, because the metal’s positive charge is reduced by delocalization of electron density from the ligand into the ligand-metal bond. But we have the distinction that with a class-a metal there is little concomitant polarization of the electron density away from the trans position of the metal. In addition, symbiosis, unlike antisymbiosis, is probably not specifically trans directional, and is just as effective in, say, tetrahedral complexes.” [7] References1. ^C. K. Jørgensen; Inorg. Chem.; 1971, 10, 1097. 2. ^R. G. Pearson, quoted in Anthony Nicholl Rail; Some reactions of a ditertiary arsine ligand; Ph.D. thesis; University College London, 1973. 3. ^J. L. Burmeister & N. J. DeStefano; Chem. Comm.; 1970, 1698. 4. ^Anthony Nicholl Rail; op. cit. 5. ^M. A. Jennings & A. Wojcicki; J. Organometal. Chem.; 1968, 14, 231. 6. ^C. K. Jørgensen; Inorg. Chem.; 1964, 3, 1201. 7. ^Anthony Nicholl Rail; op. cit. 1 : Coordination chemistry |
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