Homoleptic Cobalt and Copper Phenolate A2[M(OAr)4] Compounds: The Effect of Phenoxide Fluorination
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- 作者：Marisa C. Buzzeo ; Amber H. Iqbal ; Charli M. Long ; David Millar ; Sonal Patel ; Matthew A. Pellow ; Sahar A. Saddoughi ; Abigail L. Smenton ; John F. C. Turner ; Jay D. Wadhawan ; Richard G. Compton ; James A.
- 刊名：Inorganic Chemistry
- 出版年：2004
- 出版时间：November 29, 2004
- 年：2004
- 卷：43
- 期：24
- 页码：7709 - 7725
- 全文大小：449K
- 年卷期：v.43,no.24(November 29, 2004)
- ISSN：1520-510X
文摘
Two series of homoleptic phenolate complexes with fluorinated aryloxide ligands A2[M(OAr)4] with M = Co2+ orCu2+, OAr- = (OC6F5)- (OArF) or {3,5-OC6H3(CF3)2}- (OAr'), A+ = K (18-crown-6)+, Tl+, Ph4P+, Et3HN+, orMe4N+ have been synthesized. Two related complexes with nonfluorinated phenoxide ligands have been synthesizedand studied in comparison to the fluorinated aryloxides demonstrating the dramatic structural changes effected bymodification of OPh to OArF. The compounds {K(18-crown-6)}2[Cu(OArF)4], 1a; {K(18-crown-6)}2[Cu(OAr')4], 1b;[Tl2Cu(OArF)4], 2a; [Tl2Cu(OAr')4], 2b; (Ph4P)2[Cu(OArF)4], 3; (nBu4N)2[Cu(OArF)4], 4; (HEt3N)2[Cu(OArF)4], 5;{K(18-crown-6)}2[Cu2(
2-OC6H5)2(OC6H5)4], 6; {K(18-crown-6)}2[Co(OArF)4], 7a; {K(18-crown-6)}2[Co(OAr')4], 7b;[Tl2Co(OArF)4], 8a; [Tl2Co(OAr')4], 8b; (Me4N)2[Co(OArF)4], 9; [Cp2Co]2[Co(OAr')4], 10; and {K(18-crown-6)}2-[Co2(2-OC6H5)2(OC6H5)4], 11, have been characterized with UV-vis and multinuclear NMR spectroscopy and solutionmagnetic moment studies. Cyclic voltammetry was used to study 1a, 1b, 7a, and 7b. X-ray crystallography wasused to characterize 1b, 3, 4, 5, 6, 7a, 7b, 10, and 11. The related [MX4]2- compound (Ph4P)2[Co(OArF)2Cl2], 12,has also been synthesized and characterized spectroscopically, as well as with conductivity and single-crystalX-ray diffraction. Use of fluorinated aryloxides permits synthesis and isolation of the mononuclear, homolepticphenolate anions in good yield without oligomerized side products. The reaction conditions that result in homoleptic1a and 7a with OArF upon changing the ligand to OPh result in 2-OPh bridging phenoxides and the dimericcomplexes 6 and 11. The [M(OArF)4]2- and [M(OAr')4]2- anions in 1a, 1b, 3, 4, 5, 7a, 7b, 9, and 10 demonstratethat stable, isolable homoleptic phenolate anions do not need to be coordinatively or sterically saturated and canbe achieved by increasing the electronegativity of the ligand.
2-OC6H5)2(OC6H5)4], 6; {K(18-crown-6)}2[Co(OArF)4], 7a; {K(18-crown-6)}2[Co(OAr')4], 7b;[Tl2Co(OArF)4], 8a; [Tl2Co(OAr')4], 8b; (Me4N)2[Co(OArF)4], 9; [Cp2Co]2[Co(OAr')4], 10; and {K(18-crown-6)}2-[Co2(2-OC6H5)2(OC6H5)4], 11, have been characterized with UV-vis and multinuclear NMR spectroscopy and solutionmagnetic moment studies. Cyclic voltammetry was used to study 1a, 1b, 7a, and 7b. X-ray crystallography wasused to characterize 1b, 3, 4, 5, 6, 7a, 7b, 10, and 11. The related [MX4]2- compound (Ph4P)2[Co(OArF)2Cl2], 12,has also been synthesized and characterized spectroscopically, as well as with conductivity and single-crystalX-ray diffraction. Use of fluorinated aryloxides permits synthesis and isolation of the mononuclear, homolepticphenolate anions in good yield without oligomerized side products. The reaction conditions that result in homoleptic1a and 7a with OArF upon changing the ligand to OPh result in 2-OPh bridging phenoxides and the dimericcomplexes 6 and 11. The [M(OArF)4]2- and [M(OAr')4]2- anions in 1a, 1b, 3, 4, 5, 7a, 7b, 9, and 10 demonstratethat stable, isolable homoleptic phenolate anions do not need to be coordinatively or sterically saturated and canbe achieved by increasing the electronegativity of the ligand.