Periodic Trends and Index of Boron Lewis Acidity

Transcription

1 Periodic Trends and Index of Boron Lewis Acidity Joshua A. Plumley and Jeffrey D. Evanseck * Contribution from the Center for Computational Sciences and the Department of Chemistry and Biochemistry, Duquesne University, 600 Forbes Avenue, Pittsburgh, Pennsylvania * Corresponding author: Hevanseck@duq.eduH Supporting Information Contents Other Electronegativities Considered... 8 Figure S1: Allen... 8 Figure S2: Sanderson... 8 Figure S3: Allred Rochow... 9 Figure S4: Mulliken Jaffe... 9 Figure S Figure S Figure S Figure S Figure S Figure S Figure S Figure S Coefficients of Partial Determination Optimized Structures and Thermodynamic Data: B3LYP/6 31G(d) NH BH

2 BH 2 F BHF BF BClF BCl 2 F BCl BHCl BH 2 Cl B(OH) BH(OH) BH 2 (OH) B(CH 3 ) BH(CH 3 ) BH 2 (CH 3 ) B(SH) BH(SH) BH 2 (SH) B(SiH 3 ) BH(SiH 3 ) BH 2 (SiH 3 ) BH 3 NH BH 2 F NH BHF 2 NH BF 3 NH BClF 2 NH BCl 2 F NH BCl 3 NH BHCl 2 NH BH 2 Cl NH B(OH) 3 NH

3 BH(OH) 2 NH BH 2 (OH) NH B(CH 3 ) 3 NH BH(CH 3 ) 2 NH BH 2 (CH 3 ) NH B(SH) 3 NH BH(SH) 2 NH BH 2 (SH) NH B(SiH 3 ) 3 NH BH 2 (SiH 3 ) NH BH(SiH 3 ) 2 NH Optimized Structures and Counterpoise Corrections: QCISD(T),MP2, M06 2X NH MP2/ G(3df,2p) QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) BH MP2/ G(3df,2p) QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) BH 2 F MP2/ G(3df,2p) QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) BHF MP2/ G(3df,2p) QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) BF MP2/ G(3df,2p)

4 QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) BClF MP2/ G(3df,2p) QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) BCl 2 F MP2/ G(3df,2p) QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) BCl MP2/ G(3df,2p) QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) BHCl MP2/ G(3df,2p) QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) BH 2 Cl MP2/ G(3df,2p) QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) B(OH) M06 2X/ G(3df,2p) BH(OH) M06 2X/ G(3df,2p) BH 2 (OH) M06 2X/ G(3df,2p) B(CH 3 ) M06 2X/ G(3df,2p)

5 BH(CH 3 ) M06 2X/ G(3df,2p) BH 2 (CH 3 ) M06 2X/ G(3df,2p) B(SH) M06 2X/ G(3df,2p) BH(SH) M06 2X/ G(3df,2p) BH 2 (SH) M06 2X/ G(3df,2p) B(SiH 3 ) M06 2X/ G(3df,2p) BH(SiH 3 ) M06 2X/ G(3df,2p) BH 2 (SiH 3 ) M06 2X/ G(3df,2p) BH 3 NH MP2/ G(3df,2p) QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) BH 2 F NH MP2/ G(3df,2p) QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) BHF 2 NH MP2/ G(3df,2p) QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) BF 3 NH MP2/ G(3df,2p)

6 QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) BClF 2 NH MP2/ G(3df,2p) QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) BCl 2 F NH MP2/ G(3df,2p) QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) BCl 3 NH MP2/ G(3df,2p) QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) BHCl 2 NH MP2/ G(3df,2p) QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) BH 2 Cl NH MP2/ G(3df,2p) QCISD(T)/aug cc pvqz//mp2/ G(3df,2p) M06 2X/ G(3df,2p) B(OH) 3 NH M06 2X/ G(3df,2p) BH(OH) 2 NH M06 2X/ G(3df,2p) BH 2 (OH) NH M06 2X/ G(3df,2p) B(CH 3 ) 3 NH M06 2X/ G(3df,2p)

7 BH(CH 3 ) 2 NH M06 2X/ G(3df,2p) BH 2 (CH 3 ) NH M06 2X/ G(3df,2p) B(SH) 3 NH M06 2X/ G(3df,2p) BH(SH) 2 NH M06 2X/ G(3df,2p) BH 2 (SH) NH M06 2X/ G(3df,2p) B(SiH 3 ) 3 NH M06 2X/ G(3df,2p) BH 2 (SiH 3 ) NH M06 2X/ G(3df,2p) BH(SiH 3 ) 2 NH M06 2X/ G(3df,2p) References

8 Other Electronegativities Considered Figure S1: Allen Boron Valence Deficiency 2.0 R² = Allen Electronegativity Figure S 1. Boron s valence deficiency (electrons) vs. the average Allen electronegativitity 1 of the atoms coordinated to boron. Second and third period atoms as well as hydrogen are considered. Boron s valence deficiency is the formal valence of three minus the valence electrons predicted by NBO employing HF/cc-pVQZ//M06-2X// G(3df,2p). Figure S2: Sanderson Boron Valence Deficiency 2.0 R² = Sanderson Electronegativity Figure S 2. Boron s valence deficiency (electrons) vs. the average Sanderson electronegativitiy 2 of the atoms coordinated to boron. Second and third period atoms as well as hydrogen are considered. Boron s valence deficiency is the formal valence of three minus the valence electrons predicted by NBO employing HF/cc-pVQZ//M06-2X// G(3df,2p). 8

9 Figure S3: Allred Rochow Boron Valence Deficiency R² = Allred-Rochow Electronegativity Figure S 3. Boron s valence deficiency (electrons) vs. the average Allred-Rochow electronegativity 3 of the atoms coordinated to boron. Second and third period atoms as well as hydrogen are considered. Boron s valence deficiency is the formal valence of three minus the valence electrons predicted by NBO HF/ccpVQZ//M06-2X// G(3df,2p). Figure S4: Mulliken Jaffe Boron Valence Deficiency 2.0 R² = Mulliken-Jaffe Electronegativity Figure S 4. Boron s valence deficiency (electrons) vs. the average Mulliken-Jaffe electronegativity 4-6 of the atoms coordinated to boron. Second and third period atoms as well as hydrogen are considered. Boron s valence deficiency is the formal valence of three minus the valence electrons predicted by NBO employing HF/cc-pVQZ//M06-2X// G(3df,2p). 9

10 Figure S5 Boron Valence Deficiency BF 3 BHF 2 BH 2 F BH 2 OH B(OH) 3 BH(OH) 2 BH 3 BH 2 (CH 3 ) R² = 0.33 B(CH 3 ) 3 BH(CH 3 ) Atomic Radii Figure S 5. Boron s valence deficiency (electrons) vs. the sum of atomic radii (Å) coordinated to boron. Only second period atoms and hydrogen are considered. Boron s valence deficiency is the formal valence of three minus the valence electrons predicted by NBO employing HF/cc-pVQZ//M06-2X// G(3df,2p). Figure S6 Boron Valence Deficiency 1.0 (B) R² = BH 2 Cl BCl 3 BHCl BH 2 3 BH 2 (SH) B(SH) BH(SH)2 3 BH 2 (SiH 3 ) BH(SiH 3 ) 2 B(SiH 3 ) Atomic Radii Figure S 6. Boron s valence deficiency (electrons) vs. the sum of atomic radii (Å) coordinated to boron. Only third period atoms and hydrogen are considered. Boron s valence deficiency is the formal valence of three minus the valence electrons predicted by NBO employing HF/cc-pVQZ//M06-2X// G(3df,2p). 10

11 Figure S7 Boron Valence Deficiency 1.0 R² = BH 2 (SH) BH 2 Cl BH 3 BHCl 2 BCl 3 BH 2 (SiH 3 ) B(SH) 3 BH(SiH 3 ) 2 B(SiH3)3 BH(SH) Electronegativity Figure S 7. Boron s valence deficiency (electrons) vs. the average Pauling electronegativity of the atoms coordinated to boron. Only third period atoms and hydrogen are considered. Boron s valence deficiency is the formal valence of three minus the valence electrons predicted by NBO employing HF/cc-pVQZ//M06-2X// G(3df,2p). Figure S8 Boron Valence Deficiency BH 2 (CH 3 ) B(CH 3 ) 3 BH(CH 3 ) 2 R² = 0.68 BH 3 BH 2 (SiH 3 ) BH(SiH 3 ) 2 B(SiH 3 ) Atomic Radii Figure S 8. Boron s valence deficiency (electrons) vs. the sum of atomic radii (Å) coordinated to boron. Only Group 14 atoms (carbon periodic group) and hydrogen are considered. Boron s valence deficiency is the formal valence of three minus the valence electrons predicted by NBO employing HF/ccpVQZ//M06-2X// G(3df,2p). 11

12 Figure S9 Boron Valence Deficiency BH 2 (OH) BH(OH) 2 BH 3 BH 2 (SH) BH(SH) 2 B(SH) 3 R² = 0.76 B(OH) Electronegativity Figure S 9. Boron s valence deficiency (electrons) vs. the average Pauling electronegativity of the atoms coordinated to boron. Only Group 16 atoms (oxygen periodic group) and hydrogen are considered. Boron s valence deficiency is the formal valence of three minus the valence electrons predicted by NBO employing HF/cc-pVQZ. Figure S10 Boron Valence Deficiency BH 2 (OH) B(OH) 3 BH(OH) 2 BH 3 BH 2 (SH) Figure S 10. Boron s valence deficiency (electrons) vs. the sum of atomic radii (Å) coordinated to boron. Only Group 16 atoms (oxygen periodic group) and hydrogen are considered. Boron s valence deficiency is the formal valence of three minus the valence electrons predicted by NBO employing HF/ccpVQZ//M06-2X// G(3df,2p). 12 R² = 0.65 BH(SH) 2 B(SH) Atomic Radii

13 Figure S11 Boron Valence Deficiency 2.0 R² = BF 3 BClF 2 BHF 2 BH 2 F BCl2F BH 3 BCl 3 BH 2 Cl BHCl Electronegativity Figure S 11. Boron s valence deficiency (electrons) vs. the average Pauling electronegativity of the atoms coordinated to boron. Only Group 17 atoms (fluorine periodic group) and hydrogen are considered. Boron s valence deficiency is the formal valence of three minus the valence electrons predicted by NBO employing HF/cc-pVQZ//M06-2X// G(3df,2p). Figure S12 Boron Valence Deficiency BF 3 BHF 2 BH 2 F BClF 2 BCl 2 F BH BCl 3 3 BH 2 Cl BHCl 2 R² = Atomic Radii Figure S 12. Boron s valence deficiency (electrons) vs. the sum of atomic radii (Å) coordinated to boron. Only Group 17 atoms (fluorine periodic group) and hydrogen are considered. Boron s valence deficiency is the formal valence of three minus the valence electrons predicted by NBO employing HF/ccpVQZ//M06-2X// G(3df,2p). 13

14 Coefficients of Partial Determination 7 The coefficient of partial determination (r 2 ) has been analyzed in order to determine the importance of each independent variable (substituent electronegativity and atomic radii) when modeling the dependent variable s variance (boron s valence deficiency). The coefficient of partial determination measures the contribution of one independent variable when added to a model containing other independent variables. For example, the regarding a multiple linear regression containing a dependent variable ( ) and two independent variables ( and ) would take the following form:., Where is defined as the error sum of squares of the regression incorporating the independent variables within the parentheses. The entries to the right of the dot within the subscript of. indicate the variable that is already within the model where the entries to the left indicate the dependent variable as well as the independent variable being introduced to the model. Multiplying the result by 100 yields a percent decrease in the error sum of squares when is added to the model that already contains. Comparing coefficients of partial determination allows the importance of each variable to be assessed. For example, if is added to a model that contains only, and the error sum of squares is decreased to a greater extent than when is added to the model that contains only, than is more important than when modeling the variance of. Table S1 summarizes the coefficients of partial determination for each multiple linear regression discussed. 14

15 Table S1. Partial coefficients of determination regarding boron s valence deficiency (Y) vs. a linear combination of substituent electronegativity (EN) and atomic radii (AR). Plot.. Figure 4 a Figure 6 b Figure 7 c a Only third period atoms and hydrogen are considered. b Only group sixteen atoms (oxygen periodic group) and hydrogen are considered. c Only group seventeen atoms (fluorine periodic group) and hydrogen are considered. The data indicates that when substituent electronegativity or atomic radii is added to a model that contains the other variable, the error sum of squares decreases to about the same extent. This suggests that each is equally important when modeling the boron valence deficiency. 15

16 Optimized Structures and Thermodynamic Data: B3LYP/6 31G(d) NH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= UNPC-UNK Freq RB3LYP 6-31G(d) H3N1 PCUSER 29-Jan #N Geom=A llcheck Guess=Read SCRF=Check GenChk RB3LYP/6-31G(d) Freq H3B-NH3 0, 1 N X,1,1. H,1,B1,2,A1 H,1,B1,2,A1,3,D1,0 H,1,B1,2,A1,4,D2,0 B1= A1= D1=-120. D2=-120. Version=IA32W-G03RevD.01 Stat e=1-a1 HF= RMSD=4.490e-011 RMSF=4.317e-005 ZeroPoint= Thermal= Dipole=0.,0., DipoleDeriv= ,0., ,0., ,0., ,0., , ,0., ,0., ,0., ,0., , , , , , , , , , , , , , , , , , , Polar= ,0., , ,0., PG=C03V [C3(N1),3SGV(H1)] NImag=0 BH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= UNPC-UNK Freq RB3LYP 6-31G(d) B1H3 PCUSER 18-Dec #P Geom=A 16

17 llcheck Guess=Read SCRF=Check GenChk RB3LYP/6-31G(d) Freq Title Card Required 0,1 B H,1,B1 H,1,B2,2,A1 H,1,B3,3,A2,2,D1,0 B1= B 2= B3= A1= A2= D1=180. Ve rsion=ia32w-g03revd.01 State=1-A1' HF= RMSD=8.535e-011 RMSF =3.725e-005 ZeroPoint= Thermal= Dipole=0.,0.,0. Dipo lederiv= ,0.,0.,0., ,0.,0.,0., , ,0.,0.,0., ,0.,0.,0., , ,0., ,0., ,0., ,0., , ,0., ,0., ,0., ,0., Polar= ,0., ,0.,0., PG=D03H [O(B1),3C2(H1)] NImag=0 BH2F (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= UNPC-UNK Freq RB3LYP 6-31G(d) B1F1H2 PCUSER 15-Sep #P Geom =AllCheck Guess=Read SCRF=Check GenChk RB3LYP/6-31G(d) Freq title 0, 1 B F,1,B1 H,1,B2,2,A1 H,1,B2,2,A1,3,D1,0 B1= B2= A1= D1=180. Version=IA32W-G03RevD.01 State=1-A1 HF= RMSD=1.003e-009 RMSF=4.363e-005 ZeroPoint= Thermal= Dipole=0.,0., DipoleDeriv= ,0.,0.,0., ,0.,0.,0., , ,0.,0.,0., ,0.,0.,0., , ,0., ,0., ,0., ,0., , ,0., ,0., ,0., ,0., Polar = ,0., ,0.,0., PG=C02V [C2(B1F1),SGV(H2)] N Imag=0 BHF (Hartree/Particle) Thermal correction to Energy=

18 Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= UNPC-UNK Freq RB3LYP 6-31G(d) B1F2H1 PCUSER 15-Sep #P Geom =AllCheck Guess=Read SCRF=Check GenChk RB3LYP/6-31G(d) Freq Title Car d Required 0,1 B H,1,B1 F,1,B2,2,A1 F,1,B2,2,A1,3,D1,0 B1= B2= A1= D1=180. Version=IA32W-G03RevD.01 State =1-A1 HF= RMSD=7.274e-011 RMSF=1.623e-005 ZeroPoint= Thermal= Dipole=0.,0., DipoleDeriv= ,0., 0.,0., ,0.,0.,0., , ,0.,0.,0., ,0.,0.,0., , ,0., ,0., ,0., ,0., , ,0., ,0., ,0., ,0., Polar= ,0., ,0.,0., PG=C02V [C2(B1H1 ),SGV(F2)] NImag=0 BF BClF (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= \1\GINC-NEWTON\Freq\RB3LYP\6-31G(d)\B1F3\JOSH\19-Dec-2006\1\\#P GEOM= ALLCHECK GUESS=READ SCRF=CHECK GENCHK RB3LYP/6-31G(D) FREQ\\Title Card Required\\0,1\B\F,1,B1\F,1,B2,2,A1\F,1,B3,3,A2,2,D1,0\\B1= \ B2= \B3= \A1= \A2= \D1=180.\\V ersion=ia64-linux-g03revb.05\state=1-a1'\hf= \rmsd=7.184e-1 0\RMSF=2.767e-05\Dipole=0.,0.,0.\DipoleDeriv= ,0.,0.,0., ,0.,0.,0., , ,0.,0.,0., ,0.,0.,0., , ,0., ,0., ,0., ,0., , ,0., ,0., ,0., ,0., \Polar = ,0., ,0.,0., \PG=D03H [O(B1),3C2(F1)]\NImag =0\\

19 (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= UNPC-UNK Freq RB3LYP 6-31G(d) B1Cl1F2 PCUSER 17-Sep #P Geo m=allcheck Guess=Read SCRF=Check GenChk RB3LYP/6-31G(d) Freq title 0,1 B Cl,1,B1 F,1,B2,2,A1 F,1,B2,2,A1,3,D1,0 B1= B2= A1= D1=180. Version=IA32W-G03RevD.01 State=1-A1 HF= RMSD=2.412e-010 RMSF=5.165e-005 ZeroPoint= Thermal= Dipole=0.,0., DipoleDeriv= ,0.,0.,0., ,0.,0.,0., , ,0.,0.,0., ,0.,0.,0., , ,0., ,0., ,0., ,0., , ,0., ,0., ,0., ,0., Polar= ,0., ,0.,0., PG=C02V [C2(B1Cl1),SGV(F2)] NImag=0 BCl2F (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= UNPC-UNK Freq RB3LYP 6-31G(d) B1Cl2F1 PCUSER 17-Sep #P Geo m=allcheck Guess=Read SCRF=Check GenChk RB3LYP/6-31G(d) Freq Title Ca rd Required 0,1 B F,1,B1 Cl,1,B2,2,A1 Cl,1,B2,2,A1,3,D1,0 B1= B2= A1= D1=180. Version=IA32W-G03RevD.01 Sta te=1-a1 HF= RMSD=7.958e-010 RMSF=2.450e-005 ZeroPoint= Thermal= Dipole=0.,0., DipoleDeriv= , 0.,0.,0., ,0.,0.,0., , ,0.,0.,0., ,0.,0.,0., , ,0., ,0., ,0., ,0., , ,0., ,0., ,0., ,0., Polar= ,0., ,0.,0., PG=C02V [C2(B 1F1),SGV(Cl2)] NImag=0 19

20 BCl (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= UNPC-UNK Freq RB3LYP 6-31G(d) B1Cl3 PCUSER 10-Sep #P Geom= AllCheck Guess=Read SCRF=Check GenChk RB3LYP/6-31G(d) Freq Title Card Required 0,1 B Cl,1,B1 Cl,1,B2,2,A1 Cl,1,B3,3,A2,2,D1,0 B1= B2= B3= A1= A2= D1=180. Version=IA32W-G03RevD.01 State=1-A1' HF= RMSD=6.233e-009 RMSF=6.110e-007 ZeroPoint= Thermal= Dipole=0.,0.,0. DipoleDeriv= ,0.,0.,0., ,0.,0.,0., , ,0.,0.,0., ,0.,0.,0., , ,0., ,0., ,0., ,0., , ,0., ,0., ,0., ,0., Polar= ,0., ,0.,0., PG=D03H [O(B1),3C2(Cl1)] NImag=0 BHCl (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= UNPC-UNK Freq RB3LYP 6-31G(d) B1Cl2H1 PCUSER 15-Sep #P Geo 20

21 m=allcheck Guess=Read SCRF=Check GenChk RB3LYP/6-31G(d) Freq Title Ca rd Required 0,1 B H,1,B1 Cl,1,B2,2,A1 Cl,1,B2,2,A1,3,D1,0 B1= B2= A1= D1=180. Version=IA32W-G03RevD.01 Sta te=1-a1 HF= RMSD=8.796e-010 RMSF=1.179e-005 ZeroPoint= Thermal= Dipole=0.,0., DipoleDeriv= ,0.,0.,0., ,0.,0.,0., , ,0.,0.,0., ,0., 0.,0., , ,0., ,0., ,0., ,0., , ,0., ,0., ,0., ,0., Polar= ,0., ,0.,0., PG=C02V [C2(B 1H1),SGV(Cl2)] NImag=0 BH2Cl (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= \1\GINC-NEWTON\Freq\RB3LYP\6-31G(d)\B1Cl1H2\JOSH\15-Sep-2007\1\\#P Ge om=allcheck Guess=Read SCRF=Check GenChk RB3LYP/6-31G(d) Freq\\title\\ 0,1\B\Cl,1,B1\H,1,B2,2,A1\H,1,B2,2,A1,3,D1,0\\B1= \B2= \A1= \D1=180.\\Version=IA64L-G03RevD.01\State=1-A1\HF= \RMSD=1.051e-09\RMSF=5.720e-05\ZeroPoint= \Thermal= \Dipole=0.,0., \DipoleDeriv= ,0.,0.,0., ,0.,0.,0., , ,0.,0.,0., ,0.,0.,0., , ,0., ,0., ,0., ,0., , ,0., ,0., ,0., ,0., \Polar = ,0., ,0.,0., \PG=C02V [C2(B1Cl1),SGV(H2)] \NImag=0\\ B(OH)

22 (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= \1\GINC-PAULING\Freq\RB3LYP\6-31G(d)\B1H3O3\JOSH\26-Aug-2008\0\\#p b3 LYP/6-31G(d) freq\\title Card Required\\0,1\B,0., ,0.\O, , ,0.\H, , ,0.\O, , ,0.\H, , ,0.\O, , ,0.\H, , ,0.\\Version=IA64L-G03Rev E.01\State=1-A'\HF= \RMSD=7.205e-09\RMSF=6.583e-05\ZeroPoin t= \thermal= \dipole=0.,0.,0.\dipolederiv= , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0., 0.,0., , , ,0., , ,0.,0.,0., \Polar= , , ,0.,0., \PG=C 03H [O(B1),SGH(H3O3)]\NImag=0\\ BH(OH) (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= UNPC-UNK Freq RB3LYP 6-31G(d) B1H3O2 PCUSER 26-Aug #p b3ly P/6-31G(d) freq Title Card Required 0,1 B, , , 0. O, , ,0. H, , ,0. O, , ,0. H, , ,0. H, , ,0. Version=IA32W-G03RevE.01 State=1-A' HF= RMSD=8.275e-009 RMSF=6.576e-005 ZeroPoint= Thermal= Dipole= , ,0. DipoleDeriv= , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0., 0.,0., , , ,0., , ,0.,0.,0., Polar= , , ,0.,0., PG=C 22

23 S [SG(B1H3O2)] NImag=0 BH2(OH) (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= UNPC-UNK Freq RB3LYP 6-31G(d) B1H3O1 PCUSER 26-Aug #p b3ly P/6-31G(d) freq Title Card Required 0,1 B, , , 0. O, , ,0. H, , ,0. H, , ,0. H, , ,0. Version =IA32W-G03RevE.01 State=1-A' HF= RMSD=8.687e-009 RMSF=3.20 2e-005 ZeroPoint= Thermal= Dipole= , ,0. DipoleDeriv= , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., Polar= , , ,0.,0., PG=CS [SG(B1H3O1)] NImag=0 B(CH3)

24 BH(CH3) (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= UNPC-UNK Freq RB3LYP 6-31G(d) C3H9B1 PCUSER 22-Dec #P Geom =AllCheck Guess=Read SCRF=Check GenChk RB3LYP/6-31G(d) Freq Title Car d Required 0,1 B C,1,r1 C,1,r1,2,a1 C,1,r1,2,a1,3,d1,0 H,2,r2,1,a2,3, d2,0 H,2,r2,1,a2,3,-d2,0 H,2,r3,1,a3,3,d1,0 H,3,r2,1,a2,4,d2,0 H,3,r2, 1,a2,4,-d2,0 H,3,r3,1,a3,4,d1,0 H,4,r2,1,a2,2,d2,0 H,4,r2,1,a2,2,-d2,0 H,4,r3,1,a3,2,d1,0 r1= r2= r3= a1= a2= a3= d2= d1=180. Version =IA32W-G03RevD.01 State=1-A' HF= RMSD=5.941e-009 RMSF=3.88 7e-005 ZeroPoint= Thermal= Dipole=0.,0.,0. DipoleDeri v= ,0., ,0., ,0., ,0., , ,0., ,0., ,0., ,0., , ,0., ,0., ,0., ,0., , ,0., ,0., ,0., ,0., , , , , , , , , , , , , , , , , , , , ,0., ,0., ,0., ,0., , , , , , , , , , , , , , , , , , , , ,0., ,0., ,0., ,0., , , , , , , , , , , , , , , , , , , , ,0., ,0., ,0., ,0., Polar= ,0., , ,0., PG=C03H [O(B1),SGH(C3H3),X(H6)] NImag= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=

25 1\1\GINC-PAULING\Freq\RB3LYP\6-31G(d)\C2H7B1\JOSH\26-Aug-2008\0\\#p fr eq rb3lyp/6-31g(d)\\title Card Required\\0,1\B, , , \H, , , \C, , , \H, , , \ H, , , \H, , , \C, , , \H, , , \H, , , \H, , , \\Version=IA64L-G03RevE. 01\State=1-A\HF= \RMSD=8.490e-09\RMSF=2.875e-06\ZeroPoint= \Thermal= \Dipole= , , \Dipo lederiv= , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , \Polar= , , , , , \PG=C01 [X(C2H7B1)]\NImag=0\\ BH2(CH3) (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= \1\GINC-PAULING\Freq\RB3LYP\6-31G(d)\C1H5B1\JOSH\26-Aug-2008\0\\#p fr eq rb3lyp/6-31g(d)\\title Card Required\\0,1\B, , , \H, , , \H, , , \C, , , \H, , , \H, , , \H, , , \\Version= IA64L-G03RevE.01\State=1-A'\HF= \RMSD=4.510e-09\RMSF=2.368e- 05\ZeroPoint= \Thermal= \Dipole= , , \DipoleDeriv= , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,- 25

26 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , \Polar= , , , , , \PG=CS [SG(C1H1B1),X(H 4)]\NImag=0\\ B(SH) (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= UNPC-UNK Freq RB3LYP 6-31G(d) B1H3S3 PCUSER 26-Aug #p b3ly P/6-31G(d) freq Title Card Required 0,1 B,0., ,0. S, , ,0. H, , ,0. S, , ,0. H, , ,0. S, , ,0. H, , ,0. Version=IA32W-G03RevE. 01 State=1-A' HF= RMSD=1.560e-009 RMSF=1.326e-004 ZeroPoi nt= Thermal= Dipole=0.,0.,0. DipoleDeriv= , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0., 0.,0., Polar= , , ,0.,0., PG=C03H [O(B1),SGH(H3S3)] NImag=0 BH(SH)

27 (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= UNPC-UNK Freq RB3LYP 6-31G(d) B1H3S2 PCUSER 26-Aug #p b3ly P/6-31G(d) freq Title Card Required 0,1 B, , , 0. S, , ,0. H, , ,0. S, , ,0. H, , ,0. H, , ,0. Version=IA32W-G03RevE.01 State=1-A' HF= RMSD=1.860e-009 RMSF=1.337e-004 ZeroPoint= Thermal= Dipole= , ,0. DipoleDeriv= , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., Polar= , , ,0.,0., PG=CS [SG(B1H3S2)] NImag=0 BH2(SH) (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= UNPC-UNK Freq RB3LYP 6-31G(d) B1H3S1 PCUSER 26-Aug #p b3ly P/6-31G(d) freq Title Card Required 0,1 B, , , 0. S, , ,0. H, , ,0. H, , ,0. H, , ,0. Version =IA32W-G03RevE.01 State=1-A' HF= RMSD=1.272e-009 RMSF=8.08 7e-005 ZeroPoint= Thermal= Dipole= , ,0. DipoleDeriv= , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., Polar= , , ,0.,0., PG=CS [SG(B1H3S1)] NImag =0 27

28 B(SiH3) (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= \1\GINC-PAULING\Freq\RB3LYP\6-31G(d)\B1H9Si3\JOSH\27-Aug-2008\0\\#P G eom=allcheck Guess=Read SCRF=Check GenChk RB3LYP/6-31G(d) Freq\\Title Card Required\\0,1\B, , ,0.\Si, , ,0.\Si, , , \Si, , , \H, , ,0.\H, , , \H, , , \H, , , \H, , , \H, , , \H, , , \H, , , \H, , , \\Version=IA64L-G0 3RevE.01\State=1-A'\HF= \RMSD=5.557e-09\RMSF=1.541e-06\Zero Point= \Thermal= \Dipole= , ,0.\Dipol ederiv= , ,0., , ,0.,0.,0., , , ,0., , ,0.,0.,0., , , , , , , , , , , , , , , , , , , , , ,0., , ,0.,0.,0., , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , \Polar= , , , , , \PG=CS [SG(B1H1Si1),X(H8Si2)]\NImag=0\\ 28

29 BH(SiH3) (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= UNPC-UNK Freq RB3LYP 6-31G(d) B1H7Si2 PCUSER 27-Aug #P Geo m=allcheck Guess=Read SCRF=Check GenChk RB3LYP/6-31G(d) Freq Title Ca rd Required 0,1 B, , , H, , , Si, , , H, , , H, , , H, , , Si, , , H, , , H, , , H, , , Version=IA32W-G03RevE.01 State=1-A HF= RMSD=3.783e-009 RMSF=6.613e-006 ZeroPoint= Thermal= Dipole= , , DipoleDeriv= , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Polar= , , , , , PG=C01 [X(B1H7Si2)] NImag=0 BH2(SiH3)

30 (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= UNPC-UNK Freq RB3LYP 6-31G(d) B1H5Si1 PCUSER 27-Aug #P Geo m=allcheck Guess=Read SCRF=Check GenChk RB3LYP/6-31G(d) Freq Title Ca rd Required 0,1 B, , , H, , , H, , , Si, , , H, , , H, , , H, , , Version=IA32W-G03RevE.01 State=1-A HF= RMSD=4.752e-010 RMSF=5.972e-005 ZeroPoint= T hermal= Dipole= , , DipoleDeriv= , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Polar= , , , , , PG=C01 [X(B1H5Si1)] NImag=0 BH3 NH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies=

31 Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= UNPC-UNK Freq RB3LYP 6-31G(d) B1H6N1 PCUSER 29-Jan #N Geom =AllCheck Guess=Read SCRF=Check GenChk RB3LYP/6-31G(d) Freq H3B-NH3 0,1 B N,1,r1 H,1,r2,2,a1 H,1,r2,2,a1,3,120.,0 H,1,r2,2,a1,3,-120.,0 H, 2,r3,1,a2,3,180.,0 H,2,r3,1,a2,3,60.,0 H,2,r3,1,a2,3,-60.,0 r1= r2= r3= a1= a2= Vers ion=ia32w-g03revd.01 State=1-A1 HF= RMSD=5.146e-010 RMSF=4. 753e-005 ZeroPoint= Thermal= Dipole=0.,0., DipoleDeriv= ,0., ,0., ,0., ,0., , ,0., ,0., ,0., ,0., , ,0., ,0., ,0., ,0., , , , , , , , , , , , , , , , , , , , ,0., ,0., ,0., ,0., , , , , , , , , , , , , , , , , , , Polar= ,0., , ,0., PG=C03V [C3(B1N1),3SGV(H2)] NImag=0 BH2F NH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= UNPC-UNK Freq RB3LYP 6-31G(d) B1F1H5N1 PCUSER 15-Sep #P Ge om=allcheck Guess=Read SCRF=Check GenChk RB3LYP/6-31G(d) Freq Title C ard Required 0,1 B N,1,r1 F,1,r4,2,a3 H,1,r2,2,a1,3,d1,0 H,1,r2,2,a1, 3,-d1,0 H,2,r5,1,a4,3,180.,0 H,2,r3,1,a2,3,d2,0 H,2,r3,1,a2,3,-d2,0 r 1= r2= r3= r4= r5= a 1= a2= a3= a4= d1= d2= Version=IA32W-G03RevD.01 State=1-A' HF= RMSD=4.181e-010 RMSF=5.668e-005 ZeroPoint= Thermal= Dipole= ,0., DipoleDeriv= ,0., ,0., ,0., ,0., , ,0., ,0., ,0., ,0., , ,0., ,0., ,0., ,0., , , , , , , , , , , , , , , , , , , , ,0., ,0., ,0., ,0.,