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Abstract
A series of molybdenum complexes based on chiral C2-symmetric picchxn-type ligands (N4 ligands, defined as trans-N,N′-bis(heterocycl-2-ylmethyl)-1,2-diaminocyclohexanes) has been synthesized and characterized. Reported and novel picchxn-type ligands form (κ3-N4)Mo(CO)3, [(κ4-N4)Mo(NO)(CO)]PF6, and [(κ4-N4)Mo(NO)X]PF6 (X=Br, I) compounds. Multiple tridentate (κ3) and tetradentate (κ4) ligand configurations were observed, and the favored κ4 configuration was found to vary with N4 heterocycle identity. Heterocycle variation allowed for directed modification of the molybdenum electronic characteristics, but none of the studied {(κ4-N4)Mo(NO)}+ fragments was found to be a suitable π-base for dearomatization chemistry. The crystal structures of eight molybdenum complexes with picchxn-type ligands were determined.
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