Unusual nucleophilic reactivity of a dithiolene-based N-heterocyclic silane

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 53; no. 14; pp. 6178 - 6183
• Main Authors: Tran, Phuong M, Wang, Yuzhong, Lahm, Mitchell E, Wei, Pingrong, Schaefer, Henry F, Robinson, Gregory H
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 02.04.2024; Royal Society of Chemistry (RSC)
• Subjects: Adducts; Boron chlorides; Cleavage; Silanes
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d3dt03843b

While the dithiolene-based N-heterocyclic silane ( 4 ) reacts with two equivalents of BX 3 (X = Br, I) to give zwitterionic Lewis adducts 5 and 8 , respectively, the parallel reaction of 4 with BCl 3 results in 10, a dithiolene-substituted N-heterocyclic silane, via the Si-S bond cleavage. Unlike 5 , the labile 8 may be readily converted to 9 via BI 3 -mediated cleavage of the SiN bond. The formation of 5 and 8 confirms that 4 uniquely possesses dual nucleophilic sites: (a) the terminal sulphur atom of the dithiolene moiety; and (b) the backbone carbon of the N-heterocyclic silane unit. Dithiolene-based N-heterocyclic silane demonstrates unusual dual nucleophilic reactivity toward boron halides.