Synthesis and Reactions of Coordinatively Unsaturated Half-Sandwich Rhodium and Iridium Complexes Having a 2,6-Dimesitylbenzenethiolate Ligand

Abstract

Coordinatively unsaturated rhodium and iridium complexes bearing a bulky thiolate ligand, [Cp*M(SDmp)](BAr F 4 ) (2a, M = Rh; 2b, M = Ir; Cp* = η 5 -C 5 Me 5 ; Dmp = 2,6-(mesityl) 2 C 6 H 3 ; Ar F = 3,5-(CF 3 ) 2 C 6 H 3 ) were synthesized from the reactions of [Cp*MCl] 2 (μ-Cl) 2 with LiSDmp and NaBAr F 4 . The metal centers in 2a and 2b weakly interact with the ipso-carbon of one of the mesityl groups in the SDmp ligand, while the ipso-carbon dissociates from the coordination sphere in the reactions with donor ligands. Treatment of 2a or 2b with 2,2 0 -bipyridine (bpy) or 1,10-phenanthroline (phen) led to the formation of [Cp*M(SDmp)(bpy)](BAr F 4 ) (3a, M = Rh; 3b, M = Ir) or [Cp*M-(SDmp)(phen)](BAr F 4 ) (4a, M=Rh; 4b, M = Ir), respectively. The reactions of 2a and 2b with 2 equiv of tert-butylisocianide or 1 atm of CO gave rise to the bis-adducts [Cp*M(SDmp)(L) 2 ]-(BAr F 4 ) (5a, M=Rh, L=CN t Bu; 5b, M = Ir, L = CN t Bu; 6a, M = Rh, L=CO; 6b, M = Ir, L = CO). The coupling of terminal alkynes and SDmp took place upon the addition of excess 1-pentyne or phenylacetylene to solutions of 2a or 2b, affording cationic complexes with an S-arylated thiophene group, [Cp*M(η 4 -2, 4-R 2 C 4 H 2 S-Dmp)](BAr F 4 ) (7a, M = Rh, R = n Pr; 7b, M = Ir, R = n Pr; 7c, M = Rh, R = Ph; 7d, M = Ir, R = Ph).

Coordinatively Unsaturated [RhCp*Rf2] (Cp* = C5Me5; Rf = C6F3Cl2-3,5), General Precursor to Cp*-Diaryl and Cp*-Halo-Aryl RhIII Complexes. Observing and Testing the Effect of Cp* as Electronic Buffer

“…28 Pentacoordinated diarylated RhCp*Ar 2 derivatives have not been reported until our recent communication of 16e [RhCp*Ar 2 ] (Ar = C 6 F 5 = Pf ; Ar = C 6 F 3 Cl 2 -3,5 = Rf). 29 Finally, one amido-type C,Ncyclometalated complex [RhCp*(C−N)] 6a and the cationic [RhCp*(C−S)] + , where a 2,6-dimesitylbenzenethiolate ligand displays mesityl C1 π-coordination to Rh, 30 have also been reported.…”

Computational investigations of click-derived 1,2,3-triazoles as keystone ligands for complexation with transition metals: a review

“… 201 Furthermore, in complex 47, the Rh–N bond distance was 2.091 Å, which was in reliable agreement with those of [η 5 -Cp*Rh(2,6-(mesityl) 2 C 6 H 3 S)(bpy)][B(3,5-(CF 3 ) 2 C 6 H 3 ) 4 ]. 202 The obtained bond length values for Rh–C(Cp* centroid) in complexes 46 and 47 were in the normal range, i.e. , 1.784–1.786 Å.…”

Synthesis and Reactivity of Cp*IrIII Complexes with a C–S Chelate Displaying Metal/Sulfur Bifunctionality

“…The latter signal, ascribable to the dinuclear form, was observed almost exclusively at −50 °C, while a set of other signals appeared at above −25 °C. A decrease in the concentration of the dinuclear species was confirmed with increasing temperature, corroborating a reversible interconversion between the thiolato-bridged and 16e mononuclear thiolato complexes . A similar equilibrium in solution was observed for 1,2-benzenedithiolato complexes of CpCo III and Cp*Rh III .…”