The diradical (CH3)2CHN and its isomeric molecule (CH3)2C=HN: Generation and characterization

Abstract

A continuously flowing ͑CH 3 ͒ 2 CHN beam is generated by pyrolysis of ͑CH 3 ͒ 2 CHN 3 at 113͑Ϯ0.5͒°C using normal inlet system with an 8 mm bore of the exit of the quartz tube under the presence of molecular sieve ͑30 Å͒ and stabilizing NO gas, and its HeI photoelectron ͑PE͒ spectrum is also recorded in situ. A spectrum recorded further away from the pyrolysis catalyst or by using a 0.4 mm bore of the quartz tube is the PE spectrum of ͑CH 3 ͒ 2 CvNH, which comes from the isomerization of ͑CH 3 ͒ 2 CHN. The ionization energies of ͑CH 3 ͒ 2 CHN and ͑CH 3 ͒ 2 CvNH are determined for the first time by the photoelectron spectroscopy experiment, and Gaussian 2 and improved density functional theory calculations. Experimental and theoretical results agree reasonably well, and show that ͑CH 3 ͒ 2 CHN is a diradical with C s symmetry and has a 3 AЉ ground state, and ͑CH 3 ͒ 2 CvNH is a closed shell molecule with C s symmetry.

In Situ Investigation of the Thermal Decomposition of Cl4(CH3CN)W(NiPr) During Simulated Chemical Vapor Deposition

“…Homolysis of the W=N(imido) bond of 2 would give rise to WCl 4 and the highly reactive nitrene fragment (CH 3 ) 2 CHN ( 5 ) (Scheme ). Alkylnitrene 5 has been reported to undergo rapid isomerization to generate 2‐propanimine ( 6 ) . Therefore, the reported Raman shifts for the N=C and N‐H stretching modes of 6 were chosen as identifiers of this decomposition mechanism (1620 and 3260 cm –1 , respectively) …”