Syntheses and Structural Characterization of Tetrahedral Four-Coordinate Gold(I) Complexes of 1,3,5-Triaza-7-phosphaadamantane. An Example of a Hydrogen-Bond-Directed Supramolecular Assembly
The synthesis and structural characterization of water-soluble four-coordinate gold(I) complexes containing monodentate phosphine ligands are described. The ligands used are 1,3,5-triaza-7-phosphaadamantane (TPA) and its protonated and methylated derivatives, [HTPA]Cl and [MeTPA]I. Formation of the...
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Veröffentlicht in: | Inorganic chemistry 1996-01, Vol.35 (1), p.16-22 |
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Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | The synthesis and structural characterization of water-soluble four-coordinate gold(I) complexes containing monodentate phosphine ligands are described. The ligands used are 1,3,5-triaza-7-phosphaadamantane (TPA) and its protonated and methylated derivatives, [HTPA]Cl and [MeTPA]I. Formation of the four-coordinate gold(I) species is favored by the small cone angle of the phosphine (102°) and its ability to form a hydrogen-bonded network between the nitrogen atoms of the ligand and solvent water molecules. The gold center in all four complexes has a nearly regular tetrahedral geometry with an average P−Au−P angle of 109.5°. [(HTPA)3(TPA)Au](PF6)4·4H2O·CH3CN (1) crystallizes in the monoclinic space group P21/c (No. 14) with cell constants a = 20.719(3) Å, b = 15.606(2) Å, c = 17.854(2) Å, β = 114.03(1)°, and Z = 4. Refinement of 4977 reflections and 650 parameters yields R = 0.0396 and R w = 0.0500. [(TPA)4Au]PF6·1.5HCl·H2O (2), crystallizes in the monoclinic space group C2/c (No. 15) with cell constants a = 33.036(7) Å, b = 11.212(2) Å, c = 31.503(5) Å, b = 137.58(1)°, and Z = 8. Refinement of 3835 reflections and 470 parameters yields R = 0.0351 and R w = 0.0403. [(TPA)4Au]Cl4·6H2O (3) was characterized structurally in the cubic space group Fd3̄m (No. 227) with cell constants a = b = c = 20.020(2) Å and Z = 8. Refinement of 290 reflections and 28 parameters yields R = 0.0624 and R w = 0.1291. [(MeTPA)4Au](PF6)5·2CH3CN (4) crystallizes in the monoclinic space group C2/c (No. 15) with cell constants a = 23.337(3) Å, b = 14.855(3) Å, c = 35.317(5) Å, b = 97.95(1)°, and Z = 8. Refinement of 7840 reflections and 621 parameters yields R = 0.0493 and R w = 0.0698. |
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ISSN: | 0020-1669 1520-510X |
DOI: | 10.1021/ic950560c |