TY - JOUR
T1 - The electronic ground state of [Fe(CO)3(NO)]-
T2 - A spectroscopic and theoretical study
AU - Klein, Johannes E.M.N.
AU - Miehlich, Burkhard
AU - Holzwarth, Michael S.
AU - Bauer, Matthias
AU - Milek, Magdalena
AU - Khusniyarov, Marat M.
AU - Knizia, Gerald
AU - Werner, Hans Joachim
AU - Plietker, Bernd
PY - 2014/2/10
Y1 - 2014/2/10
N2 - 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-II species, but rather is predominantly a Fe0 species, in which the metal is covalently bonded to NO- by two π-bonds. A metal-N σ-bond is not observed. Even more complex: Spectroscopic and quantum chemical investigations show that the complex ferrate [Fe(CO) 3(NO)]- cannot be considered to be a Fe-II species, but rather is predominantly an Fe0 species, in which the metal is covalent bound to NO- by two π bonds. A metal=N σ bond is not observed.
AB - 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-II species, but rather is predominantly a Fe0 species, in which the metal is covalently bonded to NO- by two π-bonds. A metal-N σ-bond is not observed. Even more complex: Spectroscopic and quantum chemical investigations show that the complex ferrate [Fe(CO) 3(NO)]- cannot be considered to be a Fe-II species, but rather is predominantly an Fe0 species, in which the metal is covalent bound to NO- by two π bonds. A metal=N σ bond is not observed.
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U2 - 10.1002/anie.201309767
DO - 10.1002/anie.201309767
M3 - Article
C2 - 24482198
AN - SCOPUS:84893573280
SN - 1433-7851
VL - 53
SP - 1790
EP - 1794
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 7
ER -