Abstract
The interconversion of carbyne, carbyne and hydride complexes derived from protonations oftrans-[M(CNMe)2(dppe)2](M = Mo or W) has been studied. The initial site of protonation is shown to be the isonitrile nitrogen and all protonations proceed through the common carbyne intermediatetrans-[M(CNHMe)(CNMe)(dppe)2]+. The CNHMe group in traps-[M(CNHMe)2(dppe)2]2+ is shown to be susceptible to electrophilic attack at N and nucleophilic attack at ligating C, the new complexestrans-[W(CNH2Me)(CNHMe)(dppe)2](BF4)3 andtrans-[Mo(CHNHMe)(CNHMe)(dppe)2]BF4 being formed, respectively.
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