Albinati Alberto, Bovens Mike, Rüegger Heinz, Venanzi Luigi M.
Istituto di Chimica Farmaceutica, Università di Milano, I-20131 Milano, Italy, and Laboratorium für Anorganische Chemie, ETH Zürich, CH-8092 Zürich, Switzerland.
Inorg Chem. 1997 Dec 17;36(26):5991-5999. doi: 10.1021/ic970361o.
The compounds [Tp(3R,4R,5R)Ir(COD)] (COD = cycloocta-1,5-diene; Tp(3R,4R,5R) = hydrotris(pyrazolyl)borate (1), hydrotris(3-methylpyrazolyl)borate (2), hydrotris(3-isopropylpyrazolyl)borate (3), hydrotris(3,5-dimethylpyrazolyl)borate, hydrotris(3-(trifluoromethyl)-5-methylpyrazolyl)borate, hydrotris(3-phenyl-5-methylpyrazolyl)borate, hydrotris(3,5-diisopropylpyrazolyl)borate, hydrotris(3,4,5-trimethylpyrazolyl)borate, hydrotris(4-chloro-3,5-dimethylpyrazolyl)borate (9), hydrotris(4-bromo-3,5-dimethylpyrazolyl)borate) were prepared and characterized by IR and NMR spectroscopy. The X-ray crystal structure of 9.2MeOH (triclinic, space group P&onemacr; (No. 2); a = 10.044(1) Å, b = 11.186(2) Å, c = 15.499(3) Å; alpha = 77.90(1) degrees, beta = 73.23(1) degrees, gamma = 66.89(1) degrees; Z = 2; R = 0.0276 for 2469 observed reflections) shows that iridium is four-coordinate with an eta(2)-hydrotris(pyrazolyl)borate. The X-ray crystal structure of 1 (triclinic, space group P&onemacr; (No. 2); a = 7.345(1) Å, b = 7.645(1) Å, c = 15.893(5) Å; alpha = 103.17(4) degrees, beta = 90.30(2) degrees, gamma = 93.50(3) degrees; Z = 2; R = 0.0433 for 2606 observed reflections) shows that iridium is five-coordinate with an eta(3)-bonded tris(pyrazolyl)borate. Equilibria between corresponding four- (eta(2)-Tp(3R,4R,5R)) and five-coordinate (eta(3)-Tp(3R,4R,5R)) species of all the complexes are established in solution. The complex containing the ligand HB(Pz(3Me))(3) (Pz = pyrazolyl group) (2) rearranged first to the corresponding complex with HB(Pz(3Me))(2)(Pz(5Me)) and then into that with HB(Pz(3Me))(Pz(5Me))(2). However, 3, which contains HB(Pz(3)()i(Pr))(3), gave only the complex with coordinated HB(Pz(3)()i(Pr))(2)(Pz(5)()i(Pr)).
制备了化合物[Tp(3R,4R,5R)Ir(COD)]（COD = 环辛-1,5-二烯；Tp(3R,4R,5R) = 氢三(吡唑基)硼酸酯(1)、氢三(3-甲基吡唑基)硼酸酯(2)、氢三(3-异丙基吡唑基)硼酸酯(3)、氢三(3,5-二甲基吡唑基)硼酸酯、氢三(3-(三氟甲基)-5-甲基吡唑基)硼酸酯、氢三(3-苯基-5-甲基吡唑基)硼酸酯、氢三(3,5-二异丙基吡唑基)硼酸酯、氢三(3,4,5-三甲基吡唑基)硼酸酯、氢三(4-氯-3,5-二甲基吡唑基)硼酸酯(9)、氢三(4-溴-3,5-二甲基吡唑基)硼酸酯），并通过红外光谱和核磁共振光谱对其进行了表征。9·2MeOH的X射线晶体结构（三斜晶系，空间群P&onemacr; (No. 2)；a = 10.044(1) Å，b = 11.186(2) Å，c = 15.499(3) Å；α = 77.90(1)°，β = 73.23(1)°，γ = 66.89(1)°；Z = 2；对于2469个观测反射，R = 0.0276）表明铱与一个η(2)-氢三(吡唑基)硼酸酯形成四配位。1的X射线晶体结构（三斜晶系，空间群P&onemacr; (No. 2)；a = 7.345(1) Å，b = 7.645(1) Å，c = 15.893(5) Å；α = 103.17(4)°，β = 90.30(2)°，γ = 93.50(3)°；Z = 2；对于2606个观测反射，R = 0.0433）表明铱与一个η(3)-键合的三(吡唑基)硼酸酯形成五配位。在溶液中建立了所有配合物相应的四配位（η(2)-Tp(3R,4R,5R)）和五配位（η(3)-Tp(3R,4R,5R)）物种之间的平衡。含有配体HB(Pz(3Me))(3)（Pz = 吡唑基）(2)的配合物首先重排为含有HB(Pz(3Me))(2)(Pz(5Me))的相应配合物，然后再重排为含有HB(Pz(3Me))(Pz(5Me))(2)的配合物。然而，含有HB(Pz(3)()i(Pr))(3)的3只生成了与配位的HB(Pz(3)()i(Pr))(2)(Pz(5)()i(Pr))形成的配合物。
