Heterometallic dithiolene complexes formed by stepwise displacement of cyclopentadienyl ligands from nickelocene with CpMo(S2C2Ph2)2.
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.
Adams
Harry
H
Department of Chemistry, University of Sheffield, Sheffield S3 7HF, United Kingdom.
Gardner
Hannah C
HC
McRoy
Richard A
RA
Morris
Michael J
MJ
Motley
Jeffrey C
JC
Torker
Sebastian
S