195148-72-2Relevant academic research and scientific papers
Formation of the 1,4-diazabutadien-2-yl complex [Mn(CNPh*)4{C(=NPh*)C(CH3)=N(Ph*)}] through methylation of a manganese(-I) isonitrilate
Utz, Tracy L.,Leach, Patricia A.,Geib, Steven J.,Cooper, N. John
, p. 4109 - 4114 (2008/10/08)
Alkylation of [Mn(CNPh*)5]- with CH3I gives the 1,4-diazabutadien-2-yl complex [Mn-(CNPh*)4{C(=NPh*)C(CH3)=N(Ph*)}] (2) in a 30% yield, as established by a single-crystal X-ray diffraction study. The same product can be obtained in poor yield when CH3OSO2-CF3 is used as the alkylating agent, and use of ethyl iodide gives the corresponding ethyl complex [Mn(CNPh*)4{C(=NPh*)C(CH2CH 3)=N(Ph*)}] (3). It is proposed that the first step in the formation of 2 is alkylation at manganese: transient [Mn(CNPh*)5CH3] is then converted into an iminoacyl complex by isonitrile/alkyl insertion. Insertion of a second isonitrile into the metal-iminoacyl bond leads to the 1,4-diazabutadien-2-yl complex. The addition of free CNPh* to the reaction solution leads to only a modest increase in the yield of 2, but the importance of exogenous isonitrile is supported by the formation of [Mn(CNt-Bu)(CNPh*)3{C(=NPh*)C(CH 3)=N(Ph*)}] (4), in which 1 equiv of CNtBu is coordinated to Mn, when CNtBu is added to a solution of 1- before reaction with CH3I.
