Abstract
The reactions of Mn(CO) 5Br, Fe(CO) 5 and Co 2(CO) 8 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 [+1] (for Mn) or [0] (for Fe, Co) to [+2] occurred. For manganese, the Mn II species [Mn II(H 2O) 2·15-crown-5][Br −Cl −] ( 1) was obtained from the liquid clathrate layer in the reaction mixture. For iron the Fe II species [Fe IICl(H 2O)·15-crown-5][H 5O 2 +][Fe IICl 4 2−] ( 2) rapidly formed, and for cobalt the Co II species [Co II(H 2O)·15-crown-5][H 9O 4 +][Co II·15-crown-5][H 9O 4 +][Co II(H 2O)·15-crown-5][Co IICl 4 2−] 4 ( 3) was deposited from the liquid clathrate layer. It was established by X-ray crystallography that each species contains a seven-coordinate metal center with pentagonal bipyramidal stereochemistry. Complex 1 is a hydrogen-bonded single-stranded polymer through bridging halide atoms. Complex 2 has a H 5O 2 + oxonium ion hydrogen-bonded to the cations and complex 3 has a remarkable H 2O–Co 2+–H 9O 4 +–Co 2 +–H 9O 4 +–Co 2 +–H 2O cationic chain.
Published Version
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