Treatment of [(η 5 -C 5 Me 5 )Ir(η 5 -C 6 H 5 O)][BF 4 ] ( 1 ) with an excess of trialkylphosphine (PR 3 = PMe 3, PEt 3, and PMe 2 Ph) affords the η 4 -phenol tautomers [(η 5 -C 5 Me 5 )Ir(η 4 - exo -2-(PR 3 )C 6 H 5 O)][BF 4 ] ( 2 − 4 ) in which the phosphine nucleophile adds regioselectively at C-2. The X-ray molecular structure of such a phenol tautomer complex [(η 5 -C 5 Me 5 )Ir (η 4 - exo -2-(PMe 3 )C 6 H 5 O)][BF 4 ] ( 2 ) is reported. Complex 2 crystallizes in the triclinic space group P 1̄ 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)°, and Z = 2. Oxidation of these η 4 -dienone complexes 2 − 4 by iodine affords the related phosphine salts [(C 6 H 4 OH)PR 3 ][BF 4 ] ( 5 − 7 ), and the starting iridium complex is recycled in the form of [(η 5 -C 5 Me 5 )Ir(μ-I)I] 2 ·I 2 ( 8 ) as confirmed by an X-ray analysis carried out on compounds 5 and 8 . Complex 5 crystallizes in the monoclinic space group P 2 1 / c with a = 10.593(6) Å, b = 19.922(4) Å, c = 11.909(3) Å, β = 106.83(4)°, and Z = 8. The structure of 8 can be viewed as an infinite chain of dimeric iridium [(η 5 -C 5 Me 5 )Ir(μ-I)I] 2 bridged by I 2 units. Complex 8 crystallizes in the monoclinic space group P 2 1 / 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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Bras et al. (1998) studied this question.
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