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The reaction of an N‐heterocyclic phosphenium complex of manganese with MeLi/Et3NHCl under formal addition of CH4 to the Mn=P double bond can be reversed upon UV photolysis, providing a rare example for selective P−C(alkyl) bond activation. Action of LDA on the phosphenium complex does not proceed via attack at phosphorus but rather via C4‐deprotonation to yield a unique P‐analogue of an “abnormal”...
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