Aggregate Conformation 1→2 Conformation 2→3 LiCH2OCON(CH3)2m•2Et2O -20.7 N/A LiCH2OCON(CH3)2m•3Et2O -17.0 N/A LiCH2OCON(CH3)2m•2THF -18.3 N/A LiCH2OCON(CH3)2m•3THF -16.6 N/A LiCH2OCON(CH3)2d1•2Et2O -21.6 1.92 LiCH2OCON(CH3)2d1•3Et2O 3.70 -9.73 LiCH2OCON(CH3)2d1•4Et2O 3.90 -6.67 LiCH2OCON(CH3)2d1•2THF 4.77 -13.9 LiCH2OCON(CH3)2d1•3THF 11.2 -9.75 LiCH2OCON(CH3)2d1•4THF 8.35 -8.63 LiCH2OCON(CH3)2d2•2Et2O 0.858 -13.3 LiCH2OCON(CH3)2d2•3Et2O 2.92 -12.5 LiCH2OCON(CH3)2d2•4Et2O 6.97 -7.94 LiCH2OCON(CH3)2d2•2THF -22.3 11.2 LiCH2OCON(CH3)2d2•3THF 16.6 -16.2 LiCH2OCON(CH3)2d2•4THF 0.972 -4.46 LiCHPhOCON(CH3)2m•2Et2O -21.7 N/A LiCHPhOCON(CH3)2m•3Et2O -19.5 N/A LiCHPhOCON(CH3)2m•2THF -19.5 N/A LiCHPhOCON(CH3)2m•3THF -20.1 N/A LiCHPhOCON(CH3)2d1 RR•2Et2O 4.06 1.54 LiCHPhOCON(CH3)2d1 RR•2THF 4.79 -0.176 LiCHPhOCON(CH3)2d1 RS•2Et2O -5.99 -1.43 LiCHPhOCON(CH3)2d1 RS•2Et2O 2.53 -6.45 LiCHPhOCON(CH3)2d2 RR•2Et2O -9.84 1.47 LiCHPhOCON(CH3)2d2 RR•2THF -8.24 5.29 LiCHPhOCON(CH3)2d2 RS•2Et2O -14.0 4.76 LiCHPhOCON(CH3)2d2 RS•2Et2O -10.2 3.55

Table 4: Relative free energies (kcal/mol) of N-lithium and O-lithium coordination of lithium carbamate monomers and dimers in diethyl ether and THF.