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Effects of Increased Ligand Fields of the Second- and Third-Row Transition Metals on the Preferred Structures of
Yongtao Liu1, Haoyu Chen1, Jinfeng Luo1
1School of Science, Key Laboratory of High Performance Scientific Computation, Xihua University, Chengdu 610039, China.
Abstract:
The lowest-energy sandwich structures for the (C n H n )-M-(C m H m ) (n = 5, 6; m = 7, 6; m + n = 12; M = Zr to Pd and Hf to Pt) systems are all singlet or doublet spin state structures, reflecting the increased ligand-field strengths of second- and third-row transition metals relative to first-row transition metals. For Groups 7 and 8, this differs from the first-row transition metals, for which the lowest energy C12H12M sandwich structures for iron and manganese are high-spin triplet and quartet-spin state dibenzene-metal (η6-C6H6)2M (M = Fe, Mn) structures, respectively. For palladium and platinum, the lowest-energy C12H12M (M = Pd, Pt) structures have two dihapto benzene ligands coordinating to the central metal atom, each through only one of their three CC double bonds. This contrasts with the nickel C12H12Ni system, in which a singlet spin state (η6-C6H6)-Ni-(η2-C6H6) structure having one hexahapto and one dihapto benzene ligand is strongly energetically preferred. Similar doublet-spin state (η6-C6H6)-M-(η2-C6H6) (M = Co, Rh, Ir) structures are energetically preferred for the three Group 9 metals. The energetically preferred structures for all of the early transition metals are low-spin (η6-C6H6)2M and (η5-C5H5)-M-(η7-C7H7) structures, in which all 12 ring carbon atoms are bonded to the central metal atom.
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