@article {50128,
	title = {NHC-based diazo compounds: pathways to N2 liberation or dimerization},
	journal = {Journal of Organic Chemistry},
	volume = {91},
	year = {2026},
	month = {MAY },
	pages = {6566-6572},
	type = {Article},
	abstract = {<p>
	We previously reported the C-H bond cleavage of Me3SiCHN2 by 1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene (5-SIPr) to form 1. In this article, we showed that electron-poor diamido carbene 5-tBuDAC also cleaves the C-H bond of Me3SiCHN2 to form 5, unlike its ring-expanded congener 6-DippDAC, which forms N-heterocyclic methylene hydrazine. The divergence of reactivity has been explained with the help of DFT studies. Further divergence occurs when 1 and 5 were reacted with HCl. While dimerization was observed with 5-SIPr based diazoalkane to give quinoidal tetrazine (2), N2 elimination occurs from 5-tBuDAC based diazoalkane to afford 7 and 8. This contrasting behavior highlights the subtle yet profound influence of the N-heterocyclic carbene (NHC) framework on the fate of the diazo units. DFT studies shed light about the mechanism for the formation of 2 as well as reveal that N2 elimination is thermodynamically favored over dimerization for 5.</p>
},
	issn = {0022-3263},
	doi = {10.1021/acs.joc.5c03065},
	author = {Balayan, Kajal and Tiwari, Prabhakar and Sharma, Himanshu and Vanka, Kumar and Gonnade, Rajesh G. and Sen, Sakya S.}
}
