Darstellung und Charakterisierung von „Nitrenkomplexen“ des Molybdän und Wolfram der Zusammensetzung [(η⁵-C₅H₅)OM]₂(μ-NCOOC₂H₅)₂ (M = Mo, W ) und [(η⁵-C₅H₅)OMo]₂(μ-NCO₂C₂H₅)(μ-O) / Synthesis and Characterization of "Nitrene Complexes" of Molybdenum and Tungsten of Composition [(η⁵-C₅H₅)OM]₂(μ-NCOOC₂H₅)₂ (M = Mo, W ) and [(η⁵-C₅H₅)OMo]₂(μ-NCO₂C₂H₅)(μ-O)

Abstract

The photolytical reactions of η 5 -C 5 H 5 Mo(CO) 3 CH 3 (1) or η 5 -C 5 H 5 W(CO) 3 CH 3 (2) with N 3 CO 2 C 2 H 3 (3) in CH 2 Cl 2 yield the “nitrene” complexes [(η 5 -C 5 H 5 JMoO)(μ-NCO 2 C 2 H 5 ) 2 (4), [(η 5 -C 5 H 5 )WO] 2 (μ-NCO 2 C 2 H 5 ) 2 (5) and [(η-C 5 H 5 JMoO] 2 (μ-NCO 2 H 5 )(μ-O) (6) together with some η 5 -C 5 H 5 Mo(CO) 3 Cl (7) and η 5 -C 5 H 5 W(CO) 3 Cl (8), proving that the solvent takes part in the reaction. Compounds 4, 5 and 6 contain bridging imido groups, arising from the capture of probably free nitrenes NCO 2 C 2 H 5 by organometallic species. Evidence for the presence of free nitrenes in the reaction medium is provided by the isolation of urethane (9), tetrachlorethene (10), 7 and 8 as secondary products.