Stepwise Nucleophilic Substitution to Access Saturated N-heterocyclic Carbene Haloboranes with Boron–Methyl Bonds

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Compounds of boranes with N-heterocyclic carbenes are known, yet little attention has been paid to NHC compounds of boron bearing methyl and halogen moieties together. The reason can be attributed to the hazardous methyldichloroborane (MeBCl 2 ), which ignites in air. We describe here convenient solution-phase access to SIDipp·MeBCl 2 (SIDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) ( 3 ) by a salt metathesis reaction of SIDipp·BCl 3 ( 2 ) with MeLi. Replacement of the chlorine atoms of 3 with stepwise addition of AgOTf led to the formation of SIDipp·MeBCl(OTf) ( 4 ) and SIDipp·MeB(OTf) 2 ( 5 ). In the case of 4, all of the substituents on the boron atom are different. Subsequently, we extended our synthetic approach to the amidinate system and prepared PhC(N t Bu) 2 B(Me)Cl ( 7 ) from the reaction of PhC(N t Bu) 2 BCl 2 ( 6 ) with MeLi.