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Updated: Jul 18, 2026

Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
Published on: March 20, 2017
Heterometallic dithiolene complexes formed by stepwise displacement of cyclopentadienyl ligands from nickelocene with
Harry Adams1, Hannah C Gardner, Richard A McRoy
1Department of Chemistry, University of Sheffield, Sheffield S3 7HF, United Kingdom.
Abstract:
The dithiolene ligand transfer reaction between Ni(S2C2Ph2)2 (1) and CpMo(CO)3Cl (2; Cp = eta-C5H5) affords the neutral paramagnetic molybdenum bis(dithiolene) complex CpM(S2C2Ph2)2 (3), which has been structurally characterized. As found in other d1 complexes of this type, one dithiolene ligand is planar while the other is significantly folded toward the Cp ligand. An unexpected second product of the reaction is the unusual trinuclear species Ni[Mo(S2C2Ph2)2Cp]2 (4), which in the solid state contains three different dithiolene bonding modes (terminal, bridging, and semi-bridging) in the same molecule. Complex 4 can also be synthesized by displacement of the diene ligands in Ni(cod)2 with 2 equiv of 3. In contrast, the reaction of nickelocene with 3 proceeds by displacement of the Cp ligands in a stepwise manner to give initially the dinuclear species NiMo(mu-S2C2Ph2)2Cp2 5, which then reacts further with 3 to produce 4.
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