The syntheses and structures of '3+2' and '2+2+1' oxorhenium mixed-ligand complexes employing 8-hydroxy-5-nitroquinoline as the bidentate N,O donor ligand.
The syntheses and structures of '3+2' and '2+2+1' oxorhenium mixed-ligand complexes employing 8-hydroxy-5-nitroquinoline as the bidentate N,O donor ligand.
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DOI：
10.1016/s0020-1693(00)00218-8
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发表时间：
2000-10
影响因子：
2.8
通讯作者：
Xiaoyuan Chen;Frank J. Femia;J. Babich;J. Zubieta
中科院分区：
文献类型：
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作者：
Xiaoyuan Chen;Frank J. Femia;J. Babich;J. Zubieta
报道了一系列以8-羟基-5-硝基喹啉（HL）为双齿N，O给体原子体系的"3+2“和”2+2+1“混配配合物的合成和结构表征。因此，[ReOCl 3（PPh 3）2]与双阴离子三齿配体H2 Ln的一锅反应（式中H2L1=HOC6H4-2-CH = NC6H4-2-OH; H2L2=HOC6H4 -2-CH = N = C6H4-2-SH; H2L3=HOC6H4-2-CH = N = C（NHC6H5）= SH; H2L4=2-CH2OH = C5H3N-6-CH2SH; H_2L_5 =2-CO_2H <$C_5H_3N-6-CO_2H）和HL合成了一系列具有畸变八面体几何构型的[ReO（H_2Ln）（L）]_2 -6型“3+2”氧合铼配合物。1的晶体属单斜晶系，空间群C2/c，a=16.702（1），B=14.275（1），c=22.363（2）°，β=108.083（1）°，V=5068.2（7）° 3，Z=8; 2为单斜晶系，空间群P21/n，a=8.5093（4），B=38.518（2），c=11.6092（5）<$，β=97.708（1）°，V=3770.7（3）<$3，Z=8; 5的晶胞参数为：三斜晶系，空间群P1 3，Z=2。2，6-吡啶二甲醇（H2 L 6）与中间体配合物[ReOCl_2（L）（PPh_3）]（1）反应后，两个亚甲基羟基中只有一个去质子化，得到一个新的“2+2+1”配合物[ReO（OCH_3）（HL 6）（L）]·CH_3OH（7）。7的晶体数据：单斜晶系，P21/n，a=12.0579（6），B=11.0993（6），c=14.9262（8）θ，β=107.872（1）°，V=1901.2（2）θ 3，Z=8。在配合物3的制备中，观察到席夫碱H_2L_2的C → N键断裂，分离出以2-氨基苯硫酚为双阴离子配体的“2+2+1”配合物8 [ReO（PPh_3）（η2-NHC_6H_4 -2-S）（L）]·CH_2Cl_2. 8的晶体为单斜晶系，空间群C2/c，a=25.627（2），B=8.1305（6），c=31.404（2）°，β=96.147（1）°，V=6505.7（8）° 3，Z=8。在配合物6的形成过程中，HL被还原为8-羟基-5-氨基喹啉，并由此分离出一个新的配合物9，该配合物涉及来自L和8-羟基-5-氨基喹啉的两组N，O给体原子的配位，而甲氧基氧原子完成了八面体配位几何构型。9的晶体为单斜晶系，空间群为P21/n，a=7.5330（6），B=15.095（1），c=16.394（1）°，β=99.690（2）°，V=1837.7（3）° 3，Z=4。
The syntheses and structural characterizations of a series of novel ‘3+2’ and ‘2+2+1’ mixed-ligand complexes carrying 8-hydroxy-5-nitroquinoline (HL) as the bidentate N,O donor atom system are reported. Thus, one-pot reactions of [ReOCl3(PPh3)2] with dianionic tridentate ligands H2Ln(where H2L1=HOC6H4-2-CHNC6H4-2-OH; H2L2=HOC6H4-2-CHNC6H4-2-SH; H2L3=HOC6H4-2-CHNNC(NHC6H5)SH; H2L4=2-CH2OHC5H3N-6-CH2SH; and H2L5=2-CO2HC5H3N-6-CO2H) and HL afforded a series of ‘3+2’ oxorhenium complexes of the type [ReO(H2Ln)(L)] 2–6, which exhibit distorted octahedral geometries. Crystals of 1 are monoclinic, space group C2/c, a=16.702(1), b=14.275(1), c=22.363(2) Å, β=108.083(1)°, V=5068.2(7) Å3and Z=8; those of 2 are monoclinic, space group P21/n, a=8.5093(4), b=38.518(2), c=11.6092(5) Å, β=97.708(1)°, V=3770.7(3) Å3and Z=8; those of 5 are triclinic, space group P1̄, a=7.5899(8), b=10.322(1), c=11.905(1) Å, α=78.636(2)°, β=74.229(2)°, γ=71.391(2)°, V=844.3(2) Å3, and Z=2. Upon reaction of 2,6-pyridinedimethanol (H2L6) with the intermediate complex [ReOCl2(L)(PPh3)] (1), only one of the two methylene hydroxy group was deprotonated and a new ‘2+2+1’ complex [ReO(OCH3)(HL6)(L)]·CH3OH (7) was obtained. Crystal data for 7: monoclinic, P21/n, a=12.0579(6), b=11.0993(6), c=14.9262(8) Å, β=107.872(1)°, V=1901.2(2) Å3, and Z=8. In the preparation of complex 3, cleavage of the CN bond of the Schiff base H2L2was observed, and the ‘2+2+1’ complex 8 [ReO(PPh3)(η2-NHC6H4-2-S)(L)]·CH2Cl2having 2-aminothiophenol as a dianionic bidentate ligand was isolated. Crystals of 8 are monoclinic, space group C2/c, a=25.627(2), b=8.1305(6), c=31.404(2) Å, β=96.147(1)°, V=6505.7(8) Å3, and Z=8. Reduction of HL to 8-hydroxy-5-aminoquinoline was realized during the formation of complex 6, and a new complex 9 was thus isolated involving the coordination of two sets of N,O donor atoms from L and 8-hydroxy-5-aminoquinoline, while a methoxy oxygen atom completes the octahedral coordination geometry. Crystals of 9 are monoclinic, space group P21/n, a=7.5330(6), b=15.095(1), c=16.394(1) Å, β=99.690(2)°, V=1837.7(3) Å3, and Z=4.