[(N‐Lithio‐N‐mesitylsulfonyloxy‐tert‐butylcarbamate)2·(thf)3]: Crystal Structure of a Nitrenoid

The NO bond in 1 lengthens by roughly 6 pm when the neutral compound (X = H) is N-lithiated (X = Li). This key result of the first crystal structure analysis of a nitrenoid explains the facile replacement of the OR groups in nitrenoids R1(Li)OR2 by nucleophiles like R'Li and is in accord with calculational predictions. In the solid state 1 (X = Li) occurs as a Li-linked dimer with three Li-coordinating THF molecules, one of which bridges the two Li centers. R = 2,4,6-trimethylphenyl.