Transition metal complexes with heterocyclic analogs of fluorene 1. Synthesis, structures, and haptotropic rearrangements of tricarbonylchromium complexes of dibenzothiophene

Abstract

The complex formation of dibenzothiophene with chromium carbonyl complexes of the general formula L3Cr(CO)3 (L = Py, NH3, or CO) afforded η6-C12H8SCr(CO)3 (1). In the presence of tetramethylethylenediamine, complex 1 was selectively metallated with BuLi at position 4 of the coordinated ring to form η6-4-LiC12H8SCr(CO)3 (2). In decane, the tricarbonylchromium group is reversibly and intramolecularly migrates from the unsubstituted to substituted ring due to the inter-ring haptotropic rearrangement (IRHR) at 130 °C for 100 h. In decane, the rate constant of IRHR was estimated experimentally by 1H NMR spectroscopy and theoretically by the density functional theory (DFT).