During the past 10 years iron-catalyzed reactions have become established in the field of organic synthesis. For example, the complex anion Fe(CO)3(NO)~, which was originally described by Hogsed and Hieber, shows catalytic activity in various organic reactions. This anion is commonly regarded as being isoelectronic with Fe(CO)4~(2-), which, however, shows poor catalytic activity. The spectroscopic and quantum chemical investigations presented herein reveal that the complex ferrate Fe(CO)3(NO)~ cannot be regarded as a Fe~(-11) species, but rather is predominantly a Fe° species, in which the metal is covalently bonded to NO~-by two n-bonds. A metal-N o-bond is not observed.
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