Formation and Metallomimetic Reactivity of a Transient Dicoordinate Alkylborylene.

While existing literature has primarily focused on carbene-stabilized amino- and arylborylenes of the form [(carbene)BR] (R = substituent), herein we report the generation and metallomimetic reactivity of the first carbene-stabilized alkylborylene [(CAACMe)BCy] (CAACMe = 1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene, Cy = cyclohexyl. Furthermore, the transition metal-like decarbonylation reactions of a borylene complex, [(CAACMe)BCy(CO)], derived from borylene [(CAACMe)BCy] and CO, are described. Additional findings described include (i) the identification of the coordination stages of the ligand to boron towards forming complexes [(CAACMe)BCyL] in the reduction route from starting material [(CAACMe)BCyBr2] and in the photolysis route from carbonyl complex [(CAACMe)BCy(CO], and (ii) insights from quantum-chemical computations regarding the molecular and electronic structure of the borylene at various stages.

Experimental Observation of a Terminal Borylene-Dinitrogen Adduct via Cleavage of a 1,2,3,4,5-Diboratriazoline.

While azides do not react with simple alkenes except under harsh conditions, a diboron alkene analogue, the doubly cyclic alkyl(amino)carbene (CAAC)-stabilized dicyanodiborene 1, reacts spontaneously with organic azides (7-10 equiv.) at room temperature to yield two equivalents of stable CAAC-imino(cyano)boranes (2-R). NMR-spectroscopic monitoring of the reaction mixtures shows the initial formation of a 1 : 1 mixture of 2-R and a relatively long-lived intermediate (Int), which in the presence of excess azide is converted into a second equivalent of 2-R.