TY - JOUR
T1 - Cobalt Complexes with Bulky Perfluorinated Alkyl Ligands. Synthesis, Characterization, and Molecular Structure of trans-Bis(dimethylglyoximato) (pyridine) (F-isopropyl)cobalt(III)
AU - Toscano, Paul J.
AU - Brand, Holger
AU - Liu, Shuncheng
AU - Zubieta, Jon
PY - 1990/5/1
Y1 - 1990/5/1
N2 - The preparation of pyCo(DH)2[CF(CF3)2] (1) from Na[pyCo(DH)2] and (CF3)2CFI is described, where py = pyridine and DH = the monoanion of dimethylglyoxime. The Co(I) anion reagent is prepared from pyCo(DH)2Cl and 0.25 molar equiv of NaBH4. Larger proportions of reducing agent result in no isolable organocobalt(III) complex presumably due to decomposition of the alkylating agent and/or decomposition of 1 by the excess NaBH4 to give (CF3)2CFH, as demonstrated by 19F NMR spectroscopy. The reduction of 1 with NaBH4 is proposed to proceed through the intermediacy of (CF3)2CF− and Na[pyCo(DH)2] from deuterium-labeling studies. Synthetic methodology is also reported for the preparation of LCo(DH)2[CF(CF3)2], where L = H2O, 4-tert-butylpyridine (4-t-Bupy), and P(OCH3)3. Complex 1 crystallizes in the monoclinic space group P21/m, with a = 9.013 (2) Å, b = 13.524 (4) Å, c = 9.412 (2) Å, β = 101.07 (2)°, V= 1125.8 (5) Å3, and Z = 2, and was refined to R = 0.049. The structure is characterized by large distortions due to the bulky alkyl group. Comparisons are made to pyCo(DH)2[CH(CH3)2], the structure of which had previously been determined.
AB - The preparation of pyCo(DH)2[CF(CF3)2] (1) from Na[pyCo(DH)2] and (CF3)2CFI is described, where py = pyridine and DH = the monoanion of dimethylglyoxime. The Co(I) anion reagent is prepared from pyCo(DH)2Cl and 0.25 molar equiv of NaBH4. Larger proportions of reducing agent result in no isolable organocobalt(III) complex presumably due to decomposition of the alkylating agent and/or decomposition of 1 by the excess NaBH4 to give (CF3)2CFH, as demonstrated by 19F NMR spectroscopy. The reduction of 1 with NaBH4 is proposed to proceed through the intermediacy of (CF3)2CF− and Na[pyCo(DH)2] from deuterium-labeling studies. Synthetic methodology is also reported for the preparation of LCo(DH)2[CF(CF3)2], where L = H2O, 4-tert-butylpyridine (4-t-Bupy), and P(OCH3)3. Complex 1 crystallizes in the monoclinic space group P21/m, with a = 9.013 (2) Å, b = 13.524 (4) Å, c = 9.412 (2) Å, β = 101.07 (2)°, V= 1125.8 (5) Å3, and Z = 2, and was refined to R = 0.049. The structure is characterized by large distortions due to the bulky alkyl group. Comparisons are made to pyCo(DH)2[CH(CH3)2], the structure of which had previously been determined.
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U2 - 10.1021/ic00336a014
DO - 10.1021/ic00336a014
M3 - Article
AN - SCOPUS:0001635215
SN - 0020-1669
VL - 29
SP - 2101
EP - 2105
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 11
ER -