铱（I）的三（吡唑基）硼酸环辛-1,5-二烯配合物：合成研究及溶液中的平衡。一种四配位和一种五配位铱（I）三（吡唑基）硼酸配合物的X射线晶体结构

Hydrotris(pyrazolyl)borato Cycloocta-1,5-diene Complexes of Iridium(I): Synthetic Studies and Equilibria in Solution. X-ray Crystal Structures of a Four- and a Five-Coordinate Iridium(I) Hydrotris(pyrazolyl)borato Complex.

作者信息

Albinati Alberto, Bovens Mike, Rüegger Heinz, Venanzi Luigi M.

机构信息

Istituto di Chimica Farmaceutica, Università di Milano, I-20131 Milano, Italy, and Laboratorium für Anorganische Chemie, ETH Zürich, CH-8092 Zürich, Switzerland.

出版信息

Inorg Chem. 1997 Dec 17;36(26):5991-5999. doi: 10.1021/ic970361o.

DOI:10.1021/ic970361o

PMID:11670231

Abstract

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)).

摘要

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。