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1 Supporting Information Catalytic Hydrogenation of Carbon Dioxide with Ammonia-Borane by Pincer-type Phosphorus Compound: A Theoretical Prediction Guixiang Zeng, Satoshi Maeda, * Tetsuya Taketsugu, Shigeyoshi Sakaki * Contact sakaki.shigeyoshi.47e@st.kyoto-u.ac.jp smaeda@mail.sci.hokudai.ac.jp Table of Content Complete reference Page S2 Computational Details Page S3~S4 Examination of Basis Set: Page S4~S5 Procedure of the Automated Reaction Path Search Page S6 Molecular Orbital Analysis of Fragments Page S7 Geometry and energy changes for the possible reactions catalyzed the phosphorus catalysts with the ONO ligand page S8~S12 Geometry and energy changes for the possible reactions catalyzed by dib 1NP Page S13~S15 NH 2 =BH 2 and NH 3 bridged transformation of dib 4NP to dihydridophosphorane Page S18 Geometry and energy changes for the possible reactions catalyzed by Acr 1NP Page S19~S20 Molecular Orbital Analysis of Acr-TS 4NP/5NP and Acr-TS 4OP/1OP Page S21 References Page S22 Cartesian Coordinate Page S23~S122 S1

2 Reference 19 Gaussian 09, Revision D.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, S2

3 Computational Details Geometry optimizations were carried out by the density functional theory (DFT) method with the B3PW91 functional after careful examination.[s1] Frequency calculations were carried out for each stationary structure to make sure whether it is an equilibrium structure or a transition state. In this work, two kinds of basis set systems, BS I and BS II, were employed. In BS I, the 6 31+G(2d)[S2] and the 6 31+G(d,p) basis sets[s3] were employed for the phosphorus atom and other atoms, respectively. In BS II, the modified cc-pvtz basis sets[s4] were employed for the phosphorus center and the oxygen or nitrogen dentate atoms of the ligands, BH 3 NH 3, and CO 2, where the d primitive and the f primitive functions were removed from the hydrogen and heavy atoms, respectively. For other atoms, the cc-pvdz basis sets[s5] were employed. BS I was used for the geometry optimizations and frequency calculations. Each transition state was verified by the intrinsic reaction coordinate (IRC) calculation. Electronic energies were evaluated by CCSD(T) or ONIOM(CCSD(T):MP2) methods with BS II, where the reliability of BS II was carefully checked; see Table S1 and the discussion on page S5. The solvent effect of acetonitrile was evaluated with the Conductor-like Polarizable Continuum Model (CPCM) [S6] in both geometry optimizations and single-point calculations. The Gibbs energies were calculated in the same way as in our previous work,[s7] in which the entropy of translational movement was evaluated with the method developed by Whitesides et al.. [S8] The scale factor for the vibrational frequency was not employed here. The ONIOM(CCSD(T):MP2) method was employed to evaluate the electronic energy changes for the 1OP Me and dib 1NP mediated reactions, where the model calculated by the CCSD(T)/BS II method is constructed by substituting hydrogen atoms for the methyl groups in 1OP Me and dib 1NP. The CCSD(T) method was S3

4 employed to evaluate the electronic energy changes for dib 1OP, Acr 1OP, Acr 1NP catalyzed reactions, for which the main framework of the ligand is difficult to separate. Examination of Basis Set: In our previous work,[s1] BS L basis set system was employed in the CCSD(T) calculation of the model in the ONIOM(CCSD(T): MP2/cc-pVDZ); see Table S2 for details of the BS L. The model which is calculated with the CCSD(T) method in the ONIOM calculation consists of the phosphorus atom, the hydrogen substituted ONO ligand (ONO-H) in which substituents are replaced by hydrogen atoms, NH 3 BH 3, and diimine (HN=NH). In the modified cc-pvtz basis set, f orbitals are removed for heavy atoms and d orbitals are removed for hydrogen atoms. In our present work, the phosphorus compounds with conjugated framework were investigated. It is not easy to define model systems for such conjugate systems as dib 1NP, dib 1OP, Acr 1NP, and Acr 1OP. In this case, the ONIOM(CCSD(T)/BS L:MP2/cc-pVDZ) calculations cannot be performed for the large size of the reaction systems. Therefore, we made effort to reduce the number of basis sets employed for the model part in order to enable the ONIOM(CCSD(T):MP2) or CCSD(T) calculations. Here, we examined the basis set effects by employing BS II, BS III, and BS IV shown in Table S2. The transfer hydrogenation of azobenzene with NH 3 BH 3 by 1OP CF 3 was employed as the model system for basis set evaluation. The geometry changes of the 1OP CF 3 -catalyzed hydrogenation of azobenzene with NH 3 BH 3 were provided in the Supporting information in our previous work.[s1] As shown in Table S1, the electronic energy changes evaluated by BS II are similar to those by BS L. It is concluded that the use of BS II is a reasonable choice for energy evaluation. S4

5 Table S1. Basis set effects on energy changes of the transfer hydrogenation of azobenzene (7) with NH 3 BH 3 (2) by 1OP CF 3 to produce to afford NH 2 BH 2 (3) and diphenylhydrazine (10). G (in kcal/mol) BS-L BS-II BS-III BS-IV 1OP CF TS 1OP/4OP CF OP CF TS 4OP/1OP CF OP CF Table S2. Details of BS L, BS II, BS III, and BS IV. phosphorus ONO-H NH 3 BH 3 HN=NH BS-L modified cc-pvtz a modified cc-pvtz a modified cc-pvtz a modified cc-pvtz a BS-II modified cc-pvtz N, O; modified cc-pvtz modified cc-pvtz modified cc-pvtz BS-III modified cc-pvtz cc-pvdz modified cc-pvdz modified cc-pvtz BS-IV modified cc-pvtz cc-pvdz cc-pvdz cc-pvdz a The d polarization functions were removed in the basis set for hydrogen atoms and f polarization functions were removed in the basis sets for heavy atoms. S6

6 Procedure of the Automated Reaction Path Search The multiple-component artificial force induced reaction method (MC-AFIR) [S9] was employed for searching the possible reaction pathways in this work. The idea of the MC-AFIR method is to push fragments A and B together. In this study, initial mutual orientations and positions of two reactant molecules were randomly generated, and then they were pushed together by the AFIR method. In this way, the approximate product and transition state can be obtained through the optimization of the potential surface with the artificial force. Next, the approximate MC-AFIR path was re-optimized with locally updated plane (LUP) method [S10] without artificial force to get the accurate product and transition state. Then, the intrinsic reaction coordinate calculations [S11] were performed to confirm each species along the reaction route. In our work, first, we did MC-AFIR calculations on the reaction mediated by the phosphorus catalysts with the ONO ligands to search possible reaction pathways. Next, we substituted the NR(R=H or Me) group for the oxygen coordinating atom on the ONO ligand in each species, and then did full optimizations to obtain the possible reaction pathways for the reactions mediated by the phosphorus catalysts with the NNN ligands. To accelerate the search, a part of atoms were included in the fragments A and B. For the dehydrogenation step, the fragment A includes the two 5-membered rings around the phosphorus center of the phosphorus catalysts. The fragment B is NH 3 BH 3. For the transfer hydrogenation step, besides the two 5-membered rings around the phosphorus center, the hydride and proton are also involved in the fragment A. The fragment B is CO 2. S7

7 Molecular Orbital Analysis of Fragments Generally, MOs of a total system AB can be represented by a linear combination of MOs of fragments A and B; see Eq S1. ϕ i ( AB ) where i (AB ) C A ( A) C B m n ( B ) m imϕ + n inϕ = (S1) ϕ represents the i-th MO of the complex AB, ϕ (A m ) and ϕ (B n ) m-th MO and n-th MO of fragments A and B, respectively, and A C im and are the B C in are the expansion coefficients of ϕ (A m ) and ϕ (B n ), respectively. The populations of ϕ (A m ) and ϕ (B n ) can be obtained from these coefficients C andc this analysis, the transition state TS 1P/4OP is separated into two moieties, distorted 1P and NH 3 BH 3. A im B in. In S8

8 Figure S1. Geometry and energy changes of the transfer hydrogenation reaction of CO 2 with NH 3 BH 3 by 1OP Me and the formation of 4PP Me. Distances are in Å. In parentheses are Gibbs energy changes in kcal/mol. S9

9 Figure S2. Geometry and energy changes of the transfer hydrogenation reaction of CO 2 with NH 3 BH 3 by dib 1OP and the formation of dib 4PP. Distances are in Å. In parentheses are Gibbs energy changes in kcal/mol. S10

10 Figure S3. Geometry and energy changes of the transfer hydrogenation reaction of CO 2 with NH 3 BH 3 by Acr 1OP and the formation of Acr 4PP. Distances are in Å. In parentheses are Gibbs energy changes in kcal/mol. S11

11 Figure S4. Geometry and energy changes of the dehydrogenation of NH 3 BH 3 on the phosphorus center catalyzed by the phosphorus catalysts with ONO ligand. Distances are in Å. In parentheses are Gibbs energy changes in kcal/mol. Figure S5. Geometry and energy changes of the oxidative addition of the B H and N H bonds on the phosphorus center of Acr 1OP. Distances are in Å. In parentheses are Gibbs energy changes in kcal/mol. S12

12 Figure S6. Geometry and energy changes of dehydrogenation of NH 3 BH 3 catalyzed by Acr 1OP through the P C2 cooperation and P N cooperation pathways. Distances are in Å. In parentheses are Gibbs energy changes in kcal/mol. S13

13 Figure S7. Geometry and energy changes of reaction between NH 3 BH 3 and dib 1NP through the oxidative addition pathway. Distances are in Å. In parentheses are Gibbs energy changes in kcal/mol. S14

14 Figure S8. Geometry and energy changes of reaction between NH 3 BH 3 and dib 1NP through the phosphorus-ligand cooperation pathway. Distances are in Å. In parentheses are Gibbs energy changes in kcal/mol. S15

15 Figure S9. Geometry and energy changes of the formation of dib 4PP N from dib 4NP and dib 1NP. Distances are in Å. In parentheses are Gibbs energy changes in kcal/mol. S16

16 NH 2 =BH 2 and NH 3 bridged transformation of dib 4NP to dib 4PP N As shown in Figure S9, the G ο value (24.9 kcal/mol) of the NH 2 =NH 2 mediated transformation of dib 4NP to dib 4PP N is larger than that (22.7 kcal/mol) of the hydrogenation of CO 2 by dib 4NP, demonstrating that dib 4NP prefers to undergo the transfer hydrogenation reaction rather than the isomerization to dib 4PP N. As the reaction proceeds, the concentration of NH 2 =BH 2 increases, which induces oligmerization and/or polymerization. The dimerization and trimerization energies of NH 2 =BH 2 are -7.0 and -6.9 kcal/mol (CCSD(T)/BSII), respectively. In this regard, the isomerization of dib 4NP to dib 4PP N mediated by NH 2 =BH 2 becomes difficult. Recently, an ammonia (NH 3 ) bridged pathway was reported by Vanka group for the isomerization process. 19c However, the dissociation energy of NH 3 BH 3 to produce NH 3 is 27.9 kcal/mol, which is larger than the G ο value (26.4 kcal/mol) of the dehydrogenation of NH 3 BH 3 to afford NH 2 =BH 2. Therefore, NH 3 bridged transformation of dib 4NP to dib 4PP N is difficult in the present reaction system. S17

Acr 1NP through the oxidative addition pathway. Distances are in Å.

Geometry of the dimer of Acr-1NP. Distances are in Å.

17 Figure S10. Geometry and energy changes of the N H and B H bond activations by and Acr 1NP through the oxidative addition pathway. Distances are in Å. In parentheses are Gibbs energy changes in kcal/mol. Figure S11. Geometry of the dimer of Acr-1NP. Distances are in Å. Dimerization is exothermic by 0.2 kcal/mol (Electronic energy was calculated by B3PW91/BSII and the thermal correction to Gibbs energy was calculated by B3PW91/BSI). S18

18 Figure S12. Geometry and energy changes of dehydrogenation of NH 3 BH 3 by Acr 1NP through the P N and P C2 cooperation pathway. Distances are in Å. In parentheses are Gibbs energy changes in kcal/mol. S19

19 Figure S13. Geometry and energy changes of the transfer hydrogenation reaction of CO 2 with NH 3 BH 3 catalyzed by Acr 1NP. Distances are in Å. S20

20 Figure S14. Geometry and energy changes of the formation of Acr 4PP from Acr 4NP and Acr 1NP. Distances are in Å. In parentheses are Gibbs energy changes in kcal/mol. S21

Molecular Orbital Analysis of Acr-TS 4NP/5NP and Acr-TS 4OP/1OP Molecular orbital (MO) analysis of the transition states (Acr TS 4OP/1OP and Acr TS 4NP/5NP ) of the rate-determining step was

MO analysis shows that charge transfer (CT) from the HOMO consisting of the P-H σ-bonding orbital of the catalyst moiety to the LUMO (anti-bonding π*) of the CO 2 moiety plays important roles in Acr

21 Molecular Orbital Analysis of Acr-TS 4NP/5NP and Acr-TS 4OP/1OP Molecular orbital (MO) analysis of the transition states (Acr TS 4OP/1OP and Acr TS 4NP/5NP ) of the rate-determining step was performed to clarify the reason why the NNN ligand is more effective than the ONO ligand. MO analysis shows that charge transfer (CT) from the HOMO consisting of the P-H σ-bonding orbital of the catalyst moiety to the LUMO (anti-bonding π*) of the CO 2 moiety plays important roles in Acr TS 4OP/1OP and Acr TS 4NP/5NP. As shown in Scheme below, the HOMO energy is calculated to be ev in Acr 4NP, which lies at higher energy than that (-5.15 ev) of Acr 4OP. This result indicates that CT occurs from Acr 4NP to CO 2 much more strongly than that from Acr 4OP, which leads to the more stable Acr TS 4NP/5NP than Acr TS 4OP/1OP and the smaller activation energy for Acr TS 4NP/5NP than for Acr TS 4OP/1OP. Scheme S1. Important CT interactions in Acr TS 4NP/5NP and Acr-TS 4OP/1OP. S22

22 References [S1] Zeng, G.; Maeda, S.; Taketsugu, T.; S. Sakaki, Angew. Chem., Int. Ed. 2014, 53, [S2] (a) Ditchfield, R.; Hehre, W. J.; Pople, J. A. J. Chem. Phys. 1971, 54, (b) Clark, T.; Chandrasekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. J. Comp. Chem. 1983, 4, [S3] Hariharan, P. C.; Pople, J. A. Theoret. Chimica Acta 1973, 28, [S3] Dunning Jr., T. H. J. Chem. Phys. 1989, 90, [S4] Kendall, R. A.; Dunning Jr., T. H.; Harrison, R. J. J. Chem. Phys. 1992, 96, [S5] (a) Hohenberg, P.; Kohn, W. Phys. Rev. 1964, 136, B864 B871. (b) Kohn, W.; Sham, L. J. Phys. Rev. 1965, 140, A1133 A1138. [S6] (a) Tomasi, J.; Mennucci, B.; Cancès, E. J. Mol. Struct. (Theochem) 1999, 464, (b) Scalmani, G.; Frisch, M. J. J. Chem. Phys. 2010, 132, (c) Barone, V.; Cossi, M. J. Phys. Chem. A 1998, 102, (d) Cossi, M.; Rega, N.; Scalmani, G.; Barone, V. J. Comp. Chem. 2003, 24, [S7] (a) Ishikawa, A.; Nakao, Y.; Sato, H.; Sakaki, S. Inorg. Chem. 2009, 48, (b) Zeng, G.; Sakaki, S. Inorg. Chem. 2011, 50, [S8] Mammen, M.; Shakhnovich, E. I.; Deutch, J. M.; Whitesides, G. M. J. Org. Chem. 1998, 63, [S9] (a) Maeda, S.; Morokuma, K. J. Chem. Phys. 2010, 132, (b) Maeda, S.; Morokuma, K. J. Chem. Theory Comput. 2011, 7, [S10] Choi, C.; Elber, R. J. Chem. Phys. 1991, 94, [S11] Page, M.; Jr. McIver, J. W. J. Chem. Phys. 1988, 88, S23

23 Cartesian Coordinate The absolute electronic energy (in Hartree) of each molecule is provided, which is calculated by CCSD(t)/BSII or ONIOM(CCSD(t):MP2)/BSII. dib 1NP (bent) E ele (a.u. )= P N C C C C C C C C H H H C C H C C H H H S24

24 H N N C H H H C H H H dib 1NP (planar) E ele (a.u. )= P N C C C C C C C C H H S25

25 H H C H C H C C H H N N C H H H C H H H dib TS 1NP /4NP E ele (a.u. )= P N C C S26

26 C C C C C C H H H H C H C H C C H H N H H H B H H H S27

27 N N C H H H C H H H dib 4NP E ele (a.u. )= P N C C C C C C C C H H H H S28

28 C H C H C C H H N N C H H H C H H H H H dib TS 4NP/5NP E ele (a.u. )= P N C C S29

29 C C C C C C H H H C C H C C H H H H H O C O N H N C S30

30 H H H C H H H dib 5NP E ele (a.u. )= P N C C C C C C C C H H H C C H C S31

31 C H H H H H O C O N H N C H H H C H H H dib TS 5NP/1NP E ele (a.u. )= P N C C S32

32 C C C C C C H H H C C H C C H H H H H O C O N H N C S33

33 H H H C H H H dib TS 4NP/6NP Eele (a.u. )= P N C C C C C C C C H H H H C H C S34

34 H C C H H H H N H H B H H N C H H H N C H H H S35

35 dib 6NP Eele (a.u. )= P N C C C C C C C C H H H H C H C H C C H H H H N S36

36 H H B H H N N C H H H C H H H dib TS 6NP/7NP: Eele (a.u. )= P N C C C C C C C S37

37 C H H H H C H C H C C H H H H N H H B H H N N C H H S38

38 H C H H H dib 7NP Eele (a.u. )= P N C C C C C C C C H H H H C H C H C S39

39 C H H H H N H H B H H N N C H H H C H H H dib TS 7NP/4PP N Eele (a.u. )= P N C S40

40 C C C C C C C H H H H C H C H C C H H H H N H H B H S41

41 H N N C H H H C H H H dib 4PP N Eele (a.u. )= P N C C C C C C C C H H H S42

42 H C H C H C C H H N N C H H H C H H H H H dib-ts 1NP/4C2P: Eele (a.u. )= P N C S43

43 C C C C C C C H H H H C H C H C C H H N H H H B H H S44

44 H N N C H H H C H H H dib 4C2P Eele (a.u. )= P N C C C C C C C C H H H S45

45 H C H C H C C H H H H N N C H H H C H H H dib TS 1NP/4NP -apical Eele (a.u. )= P N C S46

46 C C C C C C C H H H H C H C H C C H H N H H H B H H S47

47 H N N C H H H C H H H dib-4np-apical Eele (a.u. )= P N C C C C C C C C H H H S48

48 H C H C H C C H H H H N N C H H H C H H H dib TS 1NP/4BH Eele (a.u. )= P N C S49

49 C C C C C C C H H H C C H C C H H N H H H B H H H N S50

50 N H H C H H H C H H H dib 4BH Eele (a.u. )= P N C C C C C C C C H H H S51

51 H C H C H C C H H N N C H H H C H H H H B H H N H H S52

52 H dib TS 1NP/4NH Eele (a.u. )= P N C C C C C C C C H H H C C H C C H H N H H S53

53 H B H H H N N H H C H H H C H H H dib 4NH Eele (a.u. )= P N C C C C C S54

54 C C C H H H H C H C H C C H H N N C H H H C H H H H S55

55 N H H B H H H Acr 1NP Eele (a.u. )= P N C C C C C C C C H H H C C H C S56

56 C H H C H H N H N H Acr-1NP-dimer Eele (a.u.) = (BPW91/BSII) P N C C C C C C C C H H H C S57

57 C H C C H H C H H N H N H P N C C C C C C C C H H H S58

Supporting Information. Theoretical Study of Hydrogenation Catalysis of Phosphorus Compound and

Supporting Information. Theoretical Study of Hydrogenation Catalysis of Phosphorus Compound and Supporting Information Theoretical Study of Hydrogenation Catalysis of Phosphorus Compound and Prediction of Catalyst with High Activity and Wide Application Scope Guixiang Zeng,, Satoshi Maeda,*, Tetsuya