TL;DRAbstract
Although formally forbidden, it is demonstrated that 1,3 migrations can occurnand can be facile in heterocumulenes. An investigation of this migration inna-oxoketenes showed that the 1,3 migration of the chlorine substituent in 2-nphenyl-3-oxoprop-2-enoic acid chloride is detectable below room temperature,nusing DNMR. The migration barrier derived from these DNMR experiments isn42 kJ mol-1 This is close to the reported B3LYP/6-311+G(3df,2p)//B3LYPn/6-31G* calculated value of 36 kJ mol-1. Moreover, using the B3LYP/6-311n+ G(3df,2p)//B3LYP/6-31G* method we confirmed reported G2(SVP, MP2)nmigration aptitudes. The B3LYP/6-311+G(3df,2p)//B3LYP/6-31G* migrationnbarriers are in the range 37 to 202 kJ mol-1 and differ from the G2(SVP, MP2)nvalues by p10 kJ mol-1. The substituents with lower migration barriers havenlone-pairs that may interact with the heterocumulene LUMO, and thus promotenthe migration.n A computational (B3LYP/6-311+G(3df,2p)//B3LYP/6-31G*) investigationnof the 1,3 migration i
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Although formally forbidden, it is demonstrated that 1,3 migrations can occurnand can be facile in heterocumulenes. An investigation of this migration inna-oxoketenes showed that the 1,3 migration of the chlorine substituent in 2-nphenyl-3-oxoprop-2-enoic acid chloride is detectable below room temperature,nusing DNMR. The migration barrier derived from these DNMR experiments isn42 kJ mol-1 This is close to the reported B3LYP/6-311+G(3df,2p)//B3LYPn/6-31G* calculated value of 36 kJ mol-1. Moreover, using the B3LYP/6-311n+ G(3df,2p)//B3LYP/6-31G* method we confirmed reported G2(SVP, MP2)nmigration aptitudes. The B3LYP/6-311+G(3df,2p)//B3LYP/6-31G* migrationnbarriers are in the range 37 to 202 kJ mol-1 and differ from the G2(SVP, MP2)nvalues by p10 kJ mol-1. The substituents with lower migration barriers havenlone-pairs that may interact with the heterocumulene LUMO, and thus promotenthe migration.n A computational (B3LYP/6-311+G(3df,2p)//B3LYP/6-31G*) investigationnof the 1,3 migration i
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