Carbene complexes are among the most important organometallic reagents in synthetic chemistry. They are often classified into Fischer-type carbene and Schrock-type alkylidene complexes. However, in this context, complexes formed from geminal dianions and carbenoids have gained special interest as they seem to contradict this classification pattern. Investigations have mostly concentrated on readily available bis(phosphonium) systems, thus leaving the influence of the a-substituent on the nature of the metal carbon bond unknown. We present the preparation of complexes derived from unsymmetrically substituted methandiides and Li/Cl carbenoids (e.g. 1 ) and discuss observed selectivities and properties.Lit: Schr�ter,P.; Gessner, V.H. Chem. Eur. J. 2012 , 18, 11223. Gessner, V.H. Organometallics,2011 , 30, 4228

Carbene or no carbene? Transition metal complexes from dilithio methandiides and lithium carbenoids

245th National Meeting (2013)

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