Investigation of the electronic and geometric effects of trifluoromethyl substituents on tris(pyrazolyl)borate ligands using manganese(I) and copper(I) complexes

被引:76
作者
Dias, HVR
Kim, HJ
Lu, HL
Rajeshwar, K
deTacconi, NR
DerecskeiKovacs, A
Marynick, DS
机构
[1] Dept. of Chemistry and Biochemistry, University of Texas at Arlington, Arlington
关键词
D O I
10.1021/om9600654
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Manganese tricarbonyl complexes of fluorinated tris(pyrazolyl)borate ligands [HB(3,5-(CF3)(2)Pz)(3)](-) and [HB(3-(CF3)Pz)(3)](-) (where Pz = pyrazolyl) were synthesized by treating BrMn(CO)(5) with [HB(3,5-(CF3)(2)Pz)(3)]Ag(THF) or [HB(3-(CF3)Pz)(3)]Na(THF). The reaction of [HB(3-(CF3)Pz)(3)]Na(THF) with copper(I) trifluoromethanesulfonate under CO afforded [HB(3-(CF3)Pz)(3)]CuCO. Compounds [HB(3,5-(CF3)(2)Pz)(3)]Mn(CO)(3) (5), [HB(3-(CF3)Pz)(3)]Mn(CO)(3) (6), and [HB(3-(CF3)Pz)(3)]CuCO (7) were characterized by H-1 NMR, F-19 NMR, and IR spectroscopy and by X-ray crystallography. They have relatively high C-O stretching frequencies. However, the v(CO) values are much lower than that in free CO and the relative lowering is higher for manganese adducts. The CF3 substitution on the 5-position has a significant effect on the metal center. This is readily apparent from the infrared spectroscopic data. Theoretical calculations of the geometries of [tris(pyrazolyl)borato]manganese(I) and -copper(I) carbonyls are in excellent agreement with the experimental results, increasing the degree of fluorination lengthens the metal-C and metal-N bonds and shortens the C-O distance. The metal-Pz bonding is essentially a pure sigma-interaction. Cyclic voltammetry data for the copper complexes show high oxidation potentials for the fluorinated analogs. IR spectroscopic data of the [tris(pyrazolyl)borato]manganese and -copper carbonyls have also been compared to those of cyclopentadienyl analogs.
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页码:2994 / 3003
页数:10
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