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4d vs. 5d – Reactivity and Fate of Terminal Nitrido Complexes of Rhodium and Iridium
Author(s) -
Schöffel Julia,
Šušnjar Nevena,
Nückel Stefan,
Sieh Daniel,
Burger Peter
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201000899
Subject(s) - chemistry , iridium , rhodium , intramolecular force , moiety , reactivity (psychology) , ligand (biochemistry) , medicinal chemistry , stereochemistry , yield (engineering) , amine gas treating , crystallography , catalysis , organic chemistry , medicine , biochemistry , materials science , alternative medicine , pathology , metallurgy , receptor
The stability of (pyridinediimine)rhodium– and ‐iridium–azido complexes was studied by a combination of thermoanalytical methods (DTG/MS and DSC) and DFT calculations. On a preparative scale, the isolation and X‐ray crystallographic characterization of the thermolysis products confirmed intramolecular C–H activation processes with concomitant reorganisation of C–C, C–N, N–H and Ir–N bonds to yield tuck‐in complexes with a different constitution of the ligand framework for the Rh and Ir products. The tentatively formed (Rh) or initially present (Ir) nitrido unit was converted into either an amine (Rh) or amido (Ir) moiety. Furthermore, the dimerization of the nitrido complexes to the corresponding dinitrogen compounds, i.e. 2 L n M≡N → L n M–N 2 –ML n , was investigated. Experimental evidence for the relevance of this step was provided by the isolation and X‐ray crystallographic characterization of a related dinuclear N 2 ‐bridged (pyridinediimine)dirhodium complex. DFT calculations revealed that the formation of dinitrogen complexes is thermodynamically strongly favourable and evidenced that the previous isolation of a terminal iridium–nitrido complex was possible due to a high barrier for the dimerization process and a sizeable barrier for the intramolecular C–H activation step.