New Bisphosphomide Ligands, 1,3-Phenylenebis((diphenylphosphino)methanone) [1,3-

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1 New Bisphosphomide Ligands, 1,3-Phenylenebis((diphenylphosphino)methanone) [1,3- Ph 2 PC(O)} 2 C 6 H 4 ] and (2-Bromo-1,3-phenylene)bis((diphenylphosphino)methanone) [1,3- Ph 2 PC(O)} 2 C 6 H 4 Br]: Synthesis, Coordination behavior, DFT Calculations and Catalytic Studies Pawan Kumar a, Mujahuddin M. Siddiqui a, Yerrnaidu Reddi a, Joel T Mague b, Raghavan B. Sunoj a, Marvanji S. Balakrishna a*

2 [Ru 2 (η 6 -p-cymene) 2 Cl 4 {1,3 {Ph 2 PC(O)} 2 (C 6 H 4 )}] (5) [PdCl{2,6-{Ph 2 PC(O)} 2 (C 6 H 3 )}](7) [NiBr{2,6-{Ph 2 PC(O)} 2 (C 6 H 3 )}] (8) [PdBr{2,6-{Ph 2 PC(O)} 2 (C 6 H 3 )}] (9) [Cu 2 (µ-cl) 2 {1,3-{Ph 2 PC(O)} 2 (C 6 H 4 )} 2 ] (10) [Cu 2 (µ-i) 2 {1,3-{Ph 2 PC(O)} 2 (C 6 H 4 )} 2 ] (12)

3 [Ag 2 (µ-clo 4 )(µ-cl){1,3-{ph 2 PC(O)} 2 (C 6 H 4 )} 2 ] (14) Figure S1. The optimized geometries of complexes 5, 7, 8, 9, 10, 12 and 14 at B3LYP/6-31G**, SDD level of theory. NBO Analysis Natural bonding orbital analysis provides details on the interaction between the occupied Lewis type (bond or lone pair) NBOs and unoccupied non-lewis type (anti bonding) NBOs in the molecule and which can be used as the measure of delocalization. This donor acceptor interaction can be described in terms of the second order perturbation interaction energy (E (2) ). These interaction energies are reported using the B3LYP/6-31G** and SDD for palladium metal as shown in Table S1. Table S1. The Second Order Perturbation Interaction Energies of Selected Donor and Acceptor NBOs of Palladium Pincer Complex 9 using the B3LYP Method Donor Acceptor E (2) (kcal/mol) C 1 C 51 Pd C 5 C 51 Pd P 13 Pd 61 P 14 Pd

4 P 13 Pd 61 C 51 Pd P 14 Pd 61 P 13 Pd P 14 Pd 61 C 9 P P 14 Pd 61 P 14 C P 14 Pd 61 P 14 C C 51 Pd 61 P 13 Pd C 51 Pd 61 P 14 Pd C 51 Pd 61 C 51 Pd Pd 61 C 51 Pd Pd 61 C 5 C Pd 61 P 13 Pd Pd 61 P 14 Pd The highest interaction energy is found to be kcal/mol between the donor NBO of BD (C 51 Pd 61) to acceptor NBOs of both BD* (P 13 Pd 61) and BD* (P 13 Pd 61). The over all interaction energy is found to be approximately kcal/mol. The slightly higher occupancy and good localized NBOs are obtained in P Pd bond ( electrons in both P Pd) than in C51 Pd bond ( electrons). Aim analysis Aim analysis is powerful method to explain the electron density between two atoms in the molecule. The eletron density is considered between the two atoms based on bond critical point (bcp) values

5 Table S2. Topological map showing bond paths and bond critical points for important weak interactions in palladium pincer complex 9 Bond path Interaction bcp *10-2 (a.u.) 1 Phenyl H Carbonyl O Phenyl H Carbonyl O Phosphorous and Palladium Phosphorous and Palladium Phenyl carbon and Palladium As shown in the table there are found to be two major interactions between palladium and phenyl carbon and palladium and phosphorous. The bcp of phenyl carbon and palladium is found to be higher than phosphorous and palladium atoms. Therefore the electron density is more between phenyl carbon and palladium reveals that the two atoms bind strongly. AIM analysis of Pd pincer complex 8 shows that hydrogen bonding interaction between C H O. Total electronic energies (in a.u) and Cartesian coordinates of geometries optimized at the B3LYP/6-31G*, SDD level of theory [Ru 2 (η 6 -p-cymene) 2 Cl 4 {1,3 {Ph 2 PC(O)} 2 (C 6 H 4 )}] (5) E ele = [PdCl{2,6-{Ph 2 PC(O)} 2 (C 6 H 3 )}](7) E ele =

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7 [NiBr{2,6-{Ph 2 PC(O)} 2 (C 6 H 3 )}] (8) [PdBr{2,6-{Ph 2 PC(O)} 2 (C 6 H 3 )}] (9) E ele = E ele =

8 [Cu 2 (µ-cl) 2 {1,3-{Ph 2 PC(O)} 2 (C 6 H 4 )} 2 ] (10) [Cu 2 (µ-i) 2 {1,3-{Ph 2 PC(O)} 2 (C 6 H 4 )} 2 ] (12) E ele = E ele =

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11 [Ag 2 (µ-clo 4 )(µ-cl){1,3-{ph 2 PC(O)} 2 (C 6 H 4 )} 2 ] (14) E ele =

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