Abstract
The reactions of M(CO) 6 (M=Mo, W) with HCl (g) in the presence of 15-crown-5 and H 2O in toluene have been explored. These reactions were promoted with the use of UV radiation and formed liquid clathrates almost immediately upon reaction. For each metal species, oxidation of the metal center from either [0] to [+3] in the case of Cr or from [0] to [+5] in the case of both Mo and W occurred. For chromium, a new isomer of CrCl 3(H 2O) 3 was generated in the second-sphere coordination complex, [ mer-CrCl 3(H 2O) 3·15-crown-5] ( 1), which crystallized from the liquid clathrate layer in the reaction mixture. For molybdenum and tungsten the isostructural complexes, [H 5O 2 +·15-crown-5][MOCl 4(H 2O) −], (M=Mo ( 2), M=W, ( 3)) rapidly formed where the H 5O 2 + oxonium ion was stabilized within the liquid clathrate layer. The structures of each of these complexes were established by X-ray crystallography. Complex 1 crystallizes in the monoclinic space group P2 1/ n with a=9.261(3), b=16.182(3), c=12.899(5) Å, β=107.87(1)°, V=1839 Å 3 and D calc.=1.568 g cm −3 for Z=4. Refinement based on 3217 observed reflections led to a final R value of 0.085. Complex 2 crystallizes in the monoclinic space group P2 1/ n with a=12.840(3), b=12.053(1), c=13.290(2) Å, β=94.26(3)°, V=2051 Å 3 and D calc.=1.720 g cm −3 for Z=4. Refinement based on 3208 observed reflections led to a final R value of 0.051. Complex 3 is isostructural with 2 with a=12.805(2), b=12.024(1), c=13.293(2) Å, β=94.25(1)°, V=2041 Å 3 and D calc.=2.015 g cm −3 for Z=4. Refinement based on 2543 observed reflections led to a final R value of 0.045.
Published Version
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