Experimental Sector
Computation details: All DFT calculations were accomplished with Gaussian 09[19] program package using B3LYP functional. 6-31G* basis set were used for all atoms except for Cr, which was described with LANL2DZ (ECP) basis set[20]. The Gaussian View 6.0 program was used to build the structures. Monovalent cations with quartet spin states were considered in theoretical models for the DFT study[21]. Vibrational frequencies were checked for all minima and transition states. Intrinsic reaction coordinate calculations were carried out to verify connections between transition states and different conformations. The model chosen was Cr/Me2PN(C5H9)PMe2with a cyclopentyl group attached to N, and the formation of active cationic Cr(I) specie includes reduction implication of cocatalyst from Cr(III). The Gibbs free energy collected under default conditions, and the solvent used in the calculation is methylcyclohexane.
[1] O. L. Sydora, Organometallics 2019 , 38 , 997-1010.
[2] K. A. Alferov, G. P. Belov, Y. Meng, Appl. Catal. A. Gen.2017 , 542 , 71-124.
[3] T. M. Pettijohn, W. K. Reagen, S. J. Martin, Google Patents,1994 .
[4] a) P.-A. R. Breuil, L. Magna, H. Olivier-Bourbigou, Catal. Lett. 2014 , 145 , 173-192; bJ. E. Radcliffe, A. S. Batsanov, D. M. Smith, J. A. Scott, P. W. Dyer, M. J. Hanton, ACS Catal. 2015 , 5 , 7095-7098.
[5] A. Bollmann, K. Blann, J. T. Dixon, F. M. Hess, E. Killian, H. Maumela, D. S. McGuinness, D. H. Morgan, A. Neveling, S. Otto, J. Am. Chem. Soc. 2004 , 126 , 14712-14713.
[6] T. Jiang, L. Zhang, J. Gao, C. Cao, Appl Petrochem Res2016 , 6 , 413-417.
[7] N. Bahri-Laleh, M. Karimi, Z. Kalantari, M. Fallah, A. Hanifpour, M. Nekoomanesh-Haghighi, Polym. Bull. (Berlin)2017 , 75 , 3555-3565.
[8] L. Liu, Z. Liu, R. Cheng, X. He, B. Liu, Organometallics2018 , 37 , 3893-3900.
[9] R. M. Manyik, W. E. Walker, T. Wilson, J. Catal.1977 , 47 , 197-209.
[10] J. R. Briggs, J. Chem. Soc., Chem. Commun.1989 , 674-675.
[11] aT. Agapie, J. A. Labinger, J. E. Bercaw, J. Am. Chem. Soc. 2007 , 129 , 14281-14295; bT. Agapie, S. J. Schofer, J. A. Labinger, J. E. Bercaw, J. Am. Chem. Soc. 2004 ,126 , 1304-1305.
[12] M. J. Overett, K. Blann, A. Bollmann, J. T. Dixon, D. Haasbroek, E. Killian, H. Maumela, D. S. McGuinness, D. H. Morgan,Journal of the American Chemical Society 2005 ,127 , 10723-10730.
[13] D. S. McGuinness, Chem. Rev. (Washington, DC, U. S.)2011 , 111 , 2321-2341.
[14] T. Agapie, Coord. Chem. Rev. 2011 , 255 , 861-880.
[15] J. Rabeah, M. Bauer, W. Baumann, A. E. McConnell, W. F. Gabrielli, P. B. Webb, D. Selent, A. Brückner, ACS Catal.2013 , 3 , 95-102.
[16] aI. Vidyaratne, G. B. Nikiforov, S. I. Gorelsky, S. Gambarotta, R. Duchateau, I. Korobkov, Angew. Chemie. 2009 ,121 , 6674-6678; bA. Jabri, C. B. Mason, Y. Sim, S. Gambarotta, T. J. Burchell, R. Duchateau, Angew. Chemie. Int. Ed. 2008 ,47 , 9717-9721.
[17] B. Venderbosch, J. H. Oudsen, L. A. Wolzak, D. J. Martin, T. J. Korstanje, M. Tromp, ACS Catal 2019 , 9 , 1197-1210.
[18] J. K. J. Angelika Bruckner, Ann E. C. McConnell, Paul B. Webb,Organometallics 2008 , 27 , 3849-3856.
[19] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. V. Marenich, J. Bloino, B. G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L. Sonnenberg, Williams, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery Jr., J. E. Peralta, F. Ogliaro, M. J. Bearpark, J. J. Heyd, E. N. Brothers, K. N. Kudin, V. N. Staroverov, T. A. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. P. 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, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, Wallingford, CT, 2013 .
[20] F. Alam, J. Wang, C. Dong, Q. Chang, L. Zhang, Q. Zhang, Y. Chen, T. Jiang, J. Catal. 2020 , 392 , 278-286.
[21] D.-H. Kwon, J. T. Fuller, U. J. Kilgore, O. L. Sydora, S. M. Bischof, D. H. Ess, ACS Catal. 2018 , 8 , 1138-1142.