Theoretical Study of Inverted Sandwich Type Complexes of 4d Transition Metal Elements: Interesting Similarities to and Differences from 3d Transition Metal Complexes

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 116; no. 9; pp. 2292 - 2299
• Main Authors: Kurokawa, Yusaku I, Nakao, Yoshihide, Sakaki, Shigeyoshi
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 08-03-2012
• Subjects: Density functional theory; Ground state; Niobium; Occupation; Orbitals; Periodic table; Three dimensional; Transition metals
• DOI: 10.1021/jp210781v
• EISSN: 1520-5215
• ISSN: 1089-5639

Inverted sandwich type complexes (ISTCs) of 4d metals, (μ-η6:η6-C6H6)­[M­(DDP)]2 (DDPH = 2-{(2,6-diisopropylphenyl)­amino}-4-{(2,6-diisopropylphenyl)­imino}­pent-2-ene; M = Y, Zr, Nb, Mo, and Tc), were investigated with density functional theory (DFT) and MRMP2 methods, where a model ligand AIP (AIPH = (Z)-1-amino-3-imino-prop-1-ene) was mainly employed. When going to Nb (group V) from Y (group III) in the periodic table, the spin multiplicity of the ground state increases in the order singlet, triplet, and quintet for M = Y, Zr, and Nb, respectively, like 3d ISTCs reported recently. This is interpreted with orbital diagram and number of d electrons. However, the spin multiplicity decreases to either singlet or triplet in ISTC of Mo (group VI) and to triplet in ISTC of Tc (group VII), where MRMP2 method is employed because the DFT method is not useful here. These spin multiplicities are much lower than the septet of ISTC of Cr and the nonet of that of Mn. When going from 3d to 4d, the position providing the maximum spin multiplicity shifts to group V from group VII. These differences arise from the size of the 4d orbital. Because of the larger size of the 4d orbital, the energy splitting between two dδ orbitals of M­(AIP) and that between the dδ and dπ orbitals are larger in the 4d complex than in the 3d complex. Thus, when occupation on the dδ orbital starts, the low spin state becomes ground state, which occurs at group VI. Hence, the ISTC of Nb (group V) exhibits the maximum spin multiplicity.