Homoleptic, -Bonded Octahedral [M(CO)6]2+ Cations of Iron(II), Ruthenium(II), and Osmium(II): Part 1: Synthese
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- 作者：Eduard Bernhardt ; Christian Bach ; Bianca Bley ; Rudolf Wartchow ; Ulrich Westphal ; Iona H. T. Sham ; Britta von Ahsen ; Chanqing Wang ; Helge Willner ; Robert C. Thompson ; and Friedhelm Aubke
- 刊名：Inorganic Chemistry
- 出版年：2005
- 出版时间：June 13, 2005
- 年：2005
- 卷：44
- 期：12
- 页码：4189 - 4205
- 全文大小：367K
- 年卷期：v.44,no.12(June 13, 2005)
- ISSN：1520-510X
文摘
Homoleptic octahedral, superelectrophilic 
-bonded metal carbonyl cations of the type [M(CO)6]2+ (M = Ru, Os)are generated in the Br
nsted-Lewis conjugate superacid HF/SbF5 by reductive carbonylation of M(SO3F)3 (M =Ru, Os) or OsF6. Thermally stable salts form with either [Sb2F11]- or [SbF6]- as anion, just as for the previouslyreported [Fe(CO)6]2+ cation. The latter salts are generated by oxidative (XeF2) carbonylation of Fe(CO)5 in HF/SbF5. A rationale for the two diverging synthetic approaches is provided. The thermal stabilities of [M(CO)6][SbF6]2salts, studied by DSC, range from 180 
C for M = Fe to 350 C for M = Os before decarbonylation occurs. Thetwo triads [M(CO)6][SbF6]2 and [M(CO)6][Sb2F11]2 (M = Fe, Ru, Os) are extensively characterized by single-crystalX-ray diffraction and vibrational and 13C NMR spectroscopy, aided by computational studies of the cations. Thethree [M(CO)6][SbF6]2 salts (M = Fe, Ru, Os) crystallize in the tetragonal space group P4/mnc (No. 128), whereasthe corresponding [Sb2F11]- salts are monoclinic, crystallizing in space group P21/n (No. 14). In both triads, the unitcell parameters are nearly invariant of the metal. Bond parameters for the anions [SbF6]- and [Sb2F11]- and theirvibrational properties in the two triads are completely identical. In all six salts, the structural and vibrational propertiesof the [M(CO)6]2+ cations (M = Fe, Ru, Os) are independent of the counteranion and for the most part independentof M and nearly identical. Interionic C···F contacts are similarly weak in all six salts. Metal dependency is notedonly in the 13C NMR spectra, in the skeletal M-C vibrations, and to a much smaller extent in some of the C-Ostretching fundamentals (A1g and T1u). The findings reported here are unprecedented among metal carbonyl cationsand their salts.
-bonded metal carbonyl cations of the type [M(CO)6]2+ (M = Ru, Os)are generated in the Brnsted-Lewis conjugate superacid HF/SbF5 by reductive carbonylation of M(SO3F)3 (M =Ru, Os) or OsF6. Thermally stable salts form with either [Sb2F11]- or [SbF6]- as anion, just as for the previouslyreported [Fe(CO)6]2+ cation. The latter salts are generated by oxidative (XeF2) carbonylation of Fe(CO)5 in HF/SbF5. A rationale for the two diverging synthetic approaches is provided. The thermal stabilities of [M(CO)6][SbF6]2salts, studied by DSC, range from 180 C for M = Fe to 350 C for M = Os before decarbonylation occurs. Thetwo triads [M(CO)6][SbF6]2 and [M(CO)6][Sb2F11]2 (M = Fe, Ru, Os) are extensively characterized by single-crystalX-ray diffraction and vibrational and 13C NMR spectroscopy, aided by computational studies of the cations. Thethree [M(CO)6][SbF6]2 salts (M = Fe, Ru, Os) crystallize in the tetragonal space group P4/mnc (No. 128), whereasthe corresponding [Sb2F11]- salts are monoclinic, crystallizing in space group P21/n (No. 14). In both triads, the unitcell parameters are nearly invariant of the metal. Bond parameters for the anions [SbF6]- and [Sb2F11]- and theirvibrational properties in the two triads are completely identical. In all six salts, the structural and vibrational propertiesof the [M(CO)6]2+ cations (M = Fe, Ru, Os) are independent of the counteranion and for the most part independentof M and nearly identical. Interionic C···F contacts are similarly weak in all six salts. Metal dependency is notedonly in the 13C NMR spectra, in the skeletal M-C vibrations, and to a much smaller extent in some of the C-Ostretching fundamentals (A1g and T1u). The findings reported here are unprecedented among metal carbonyl cationsand their salts.