Aminolysis of Dicationic Ruthenium Thiophene Complexes

Aminolysis of iridium thiophene compounds

“…The addition and C-S cleavage processes occur regiospecifically at the (Me)S-C linkage. The presence of only one isomer for derivatives 12-17 was established by 1 The iminum carbon is demonstrably electrophilic, because it is susceptible to base hydrolysis attack, as observed for ruthenium analogue species. 1 Partial recyclization of the thiophene ligand proceeds in the thermodynamic compound 12 in presence of triflic acid.…”

“…The presence of only one isomer for derivatives 12-17 was established by 1 The iminum carbon is demonstrably electrophilic, because it is susceptible to base hydrolysis attack, as observed for ruthenium analogue species. 1 Partial recyclization of the thiophene ligand proceeds in the thermodynamic compound 12 in presence of triflic acid. It is known that the kinetic isomers of the ruthenium analogues are rapidly transformed after treatment with protic sources.…”

“…These iminium centers are conjugated via a π-bonding network with the rest of the allylthiolate, where the highest delocalization was observed for compound 12, and similar behavior has been reported for the aminolysis of dicationic ruthenium thiophene compounds. 1 The distances of Ir(1)-S(1) and S(1)-C(1) are decreasing in the following order: 12 > 14 > 13 and 14 > 12 > 13, respectively. The piperidine and morpholine fragments showed a chair conformation and the pyrrolidine, an envelope one.…”

“…It is known that the kinetic isomers of the ruthenium analogues are rapidly transformed after treatment with protic sources. 1 The iridium compound 13 showed faster interconversion between kinetic and thermodynamic products, which did not allow to compare the reactivity of the kinetic isomer with the ruthenium analogue. Attempts to remove the Cp*Ir fragment from compound 13 were carried out in presence of (n-Bu 4 )NCl or MeOTf unsuccessfully, which suggest the high stability of the η 3 -allyl-Ir bond.…”

Acid—Base Chemistry of Transition-Metal—π-Thiophene Complexes

“…Dicationic π-thiophene complexes react efficiently with ammonia and amines to give monocations resulting from the net addition of NRH* (26). The tetramethylthiophene complexes (CsMe5)Rh(GiMe4S) 2+ and (arene)Ru(C4Me4S) 2+ are the exception: they give ring adducts resulting from the addition of NHR-without C-S scission, i.e., the products are (ring)M(2-H2~ NC4Me4S)+.…”