The structures and stability of pentacoordinate germylenoid PhCH2(NH2)CH3GeLiF

The structures and stability of pentacoordinate germylenoid PhCH2(NH2)CH3GeLiF were first theoretically studied by density functional theory. Two equilibrium structures, the three-membered ring and the p-complex structures, were located. The three-membered ring structure is more stable both in vacuum and in solvents (ether, THF, and acetone). The Ge-N coordination energies at the B3LYP/6-311+G(d,p) level are 35.8 and 7.9 kJ/mol in the three-membered ring and the p-complex structures, respectively. The insertion reactions with CH3F indicate that germylenoid PhCH2(NH2)CH3GeLiF is more stable than germylene PhCH2(NH2)CH3Ge. The insertion barrier of PhCH2(NH2)CH3GeLiF with CH3F is higher than that of PhCH3CH3GeLiF, indicating that the amine coordination make PhCH2(NH2)CH3GeLiF more stable.