| Abstract
| - Treatment of [(η5-C5Me5)Ir(η5-C6H5O)][BF4] (1) with trialkyl phosphine (PR3 = PMe3, PEt3, PMe2Ph) affords the η4-phenol tautomers [(η5-C5Me5)Ir(η4-exo-2-(PR3)-C6H5O)][BF4] 2−4; the X-ray molecular structure of the phenol tautomer complex 2 is reported; oxidation of these η4-dienone complexes by iodine affords the related phosphine salts [(C6H4OH)PR3][BF4] 5−7 and the starting iridium complex recycled in the form of [(η5-C5Me5)Ir(μ-I)I]2·I2 (8).
- Treatment of [(η5-C5Me5)Ir(η5-C6H5O)][BF4] (1) with an excess of trialkylphosphine (PR3 = PMe3, PEt3, andPMe2Ph) affords the η4-phenol tautomers [(η5-C5Me5)Ir(η4-exo-2-(PR3)C6H5O)][BF4] (2−4) in which the phosphinenucleophile adds regioselectively at C-2. The X-ray molecular structure of such a phenol tautomer complex[(η5-C5Me5)Ir (η4-exo-2-(PMe3)C6H5O)][BF4] (2) is reported. Complex 2 crystallizes in the triclinic space groupP1̄ with a = 8.599(1) Å, b = 9.0173(9) Å, c = 14.448(3) Å, α = 95.90(1)°, β = 99.47(1)°, γ = 99.20(1)°, andZ = 2. Oxidation of these η4-dienone complexes 2−4 by iodine affords the related phosphine salts [(C6H4OH)PR3][BF4] (5−7), and the starting iridium complex is recycled in the form of [(η5-C5Me5)Ir(μ-I)I]2·I2 (8) asconfirmed by an X-ray analysis carried out on compounds 5 and 8. Complex 5 crystallizes in the monoclinicspace group P21/c with a = 10.593(6) Å, b = 19.922(4) Å, c = 11.909(3) Å, β = 106.83(4)°, and Z = 8. Thestructure of 8 can be viewed as an infinite chain of dimeric iridium [(η5-C5Me5)Ir(μ-I)I]2 bridged by I2 units.Complex 8 crystallizes in the monoclinic space group P21/c with a = 15.533(3) Å, b = 8.374(1) Å, c = 23.541(4)Å, β = 100.89(4)°, and Z = 4.
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