Dichalcogenide Cleavage and Carbonyl Insertion Reactions on a Dirhodium Bond

Abstract

AbstractThe reaction of the binuclear rhodium complex [(η−C5H5)2Rh2(μ‐CO)(μ‐η1:η1‐C2(CF3)2)] with a series of dichalcogenides, R2E2 (E = S, Se, Te; R = Me, Et, i‐Pr, Ph, Fc; not all combinations) has provided mixtures of complexes, the majority of which have been characterized by standard spectroscopic techniques. These complexes arise as a consequence of carbonyl substitution followed by chalcogen‐chalcogen bond cleavage giving [(η−C5H5)2Rh2(μ‐ER)2(μ‐η1:η1‐C2(CF3)2)], possibly concomitant with CO insertion into a Rh‐C2(CF3)2 bond of the product in some cases, giving [(η−C5H5)2Rh2(CO)(μ‐ER)2(μ‐η1:η1‐C2(CF3)2C(O))] (E = Se, Te; R = Me, Et, i‐Pr, Ph, Fc; not all combinations). In the case of Te2R2 the dichalcogenide products have been structurally characterized for the carbonyl insertion product (for R = Et) and the simple cleavage case (for R = i‐Pr). In both, the putative m‐symmetry is broken by substituent dispositions and, in the R = Et adduct, torsion in the fluorocarbon skeleton.