title: Spin-Orbit Coupling and Outer-Core Correlation Effects in Ir- and Pt-Catalyzed C-H Activation.
abstract: The transition metal-dependent spin-orbit coupling (SOC) and outer-core (5s5p) correlation effects in Ir- and Pt-catalyzed C-H activation processes are studied here using high level ab initio computations. The catalysts involve complexes with oxidation states: Ir(I), Ir(III), Pt(0), and Pt(II). It is demonstrated that for these heavy 5d transition metal-containing systems, the SOC effect and outer-core correlation effect on C-H activation are up to the order of ∼1 kcal/mol, and should be included if chemical accuracy is aimed. The interesting trends in our studied systems are: (1) the SOC effect consistently increases the C-H activation barriers and is apparently larger in higher oxidation states (Pt(II) and Ir(III)) than in low-oxidation states (Pt(0) and Ir(I)); and (2) the magnitude of outer-core (5s5p) correlation effects is larger in less coordinate-saturated system. The effect of basis set on the outer-core correlation correction is significant; larger basis sets tend to increase the C-H activation barriers.
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences , Beijing, 100190, China.|Key Laboratory of Green Chemical Technology of College of Heilongjiang Province, College of Chemical and Environmental Engineering, Harbin University of Science and Technology , Harbin 150080, China.
authors.forename: Kejuan
authors.initials: K
authors.lastname: Chen
authors.affiliation: Key Laboratory of Green Chemical Technology of College of Heilongjiang Province, College of Chemical and Environmental Engineering, Harbin University of Science and Technology , Harbin 150080, China.
authors.forename: Guiling
authors.initials: G
authors.lastname: Zhang
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences , Beijing, 100190, China.
authors.forename: Hui
authors.initials: H
authors.lastname: Chen
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences , Beijing, 100190, China.
authors.forename: Jiannian
authors.initials: J
authors.lastname: Yao
authors.affiliation: Institute of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem , Givat Ram Campus, 91904 Jerusalem, Israel.
authors.forename: David
authors.initials: D
authors.lastname: Danovich
authors.affiliation: Institute of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem , Givat Ram Campus, 91904 Jerusalem, Israel.
authors.forename: Sason
authors.initials: S
authors.lastname: Shaik