Substituent effects on structure, stability, chemical reactivity of new (nitrenoethynyl)alkylgermylenes at theoretical study

Experimentally unreachable reactive intermediates of (nitrenoethynyl)-X-germylenes were compared and contrasted at B3LYP, HF, MP2, MP4, CCSD, and QCISD(T) levels with 6-311++G(d,p) basis set (X– Ge –C≡C–N; X = H (1), Me (2), Et (3), Pr (4), i-Pr (5), and t-Bu (6)). The effect of small and large groups on these acetylene linked reactive intermediates were studied. All singlet (nitrenoethynyl)-X-germylene species were identified as ground states with one local closed-shell singlet germylene subunit (δ2π0) and one local closed-shell singlet nitrene subunit (π2π0) were coupled through acetylene linkage. Also, one local closed-shell singlet germylene subunit (δ2π0) and one local triplet nitrene subunit (π1π1) were connected to make triplet (nitrenoethynyl)germylenes. Quintet states were found as the most unstable species with one local triplet divalency subunit (π 1π1) and also other local triplet nitrene subunit (π1π1). The species of (nitrenoethynyl)germylenes could be applied as dipolar intermediates in mechanism identification of chemical reactions.

Keywords:

Nitrenoethynyl)germylenes , steric effects , acetylene linkage , theoretical study