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Several N-Heterocyclic Carbene (NHC)-boryl sulfides with B-substituents were prepared. The added steric hindrance leads to much improved selectivities as only the NHC-boryl mono-sulfides were obtained. The B-substituted NHC-boranes are also conducive to more selective S to N NHC-boryl shift, provided that the NHC used is not too sterically demanding.

Graphical abstract: Thiolation of NHC-boranes: influence of the substitution at boron

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