Catalytic Cyclooligomerization of Thietane by Dirhenium Carbonyl Complexes

Recent Development of Rhenium-Catalyzed Organic Synthesis

“…The trirhenium complex Re 3 (CO) 10 (µ-thietane)(µ-H ) 3 was first found to be the effective catalysts for the cyclooligomerization of thietanes to produce cyclotrimer, cyclotetramer and cyclohexamer of thietanes [70]. They then investigated the same cyclooligomerization in the presence of Re 2 (CO) 10 , Re 2 (CO) 9 (NCMe) and some other sulfur-coordinated dirhenium carbonyl complexes which prepared from the reaction of Re 2 (CO) 9 (NCMe) with sulfurcycles such as thietane and 1,5,9-trithiacyclododecane, and found that these complexes also show catalytic activity [71]. For example, Re 2 (CO) 9 (thietane) and Re 2 (CO) 8 (PMe 2 Ph)(thietane) were found to display the good catalytic activity for the cyclooligomerization of thietane to give cyclotrimer, cyclohexamer (Scheme 47) [71].…”

“…They then investigated the same cyclooligomerization in the presence of Re 2 (CO) 10 , Re 2 (CO) 9 (NCMe) and some other sulfur-coordinated dirhenium carbonyl complexes which prepared from the reaction of Re 2 (CO) 9 (NCMe) with sulfurcycles such as thietane and 1,5,9-trithiacyclododecane, and found that these complexes also show catalytic activity [71]. For example, Re 2 (CO) 9 (thietane) and Re 2 (CO) 8 (PMe 2 Ph)(thietane) were found to display the good catalytic activity for the cyclooligomerization of thietane to give cyclotrimer, cyclohexamer (Scheme 47) [71]. Compared to the use of trirhenium complex Re 3 (CO) 10 [µ-thietane](µ-H) 3 , Re 2 (CO) 9 (thietane)-catalyzed cyclooligomerization shows much higher selectivity for cyclotrimer.…”

2,9-Bis(methoxymethyl)-1,3,8,10-tetrathiacyclotetradecane

“…Polyether macrocycles or thiacrowns, as they are commonly called, constitute an extensive family of large-ring heterocycles. Strained ring thioethers have been used for the preparation of thiacrown ethers such as thietane and thiirane reagents (Adams & Falloon, 1994, 1995Adams et al, 1997).…”

Synthetic, structural, spectroscopic, and electrochemical studies of mixed sandwich Rh(III) and Ir(III) complexes involving Cp* and tridentate macrocycles

“…More recent work with these types of macrocyclic ligands includes the examination of their organometallic chemistry [4][5][6][7][8][9][10][11][12][13][14]. The two macrocycles can be compared to g 5 -cyclopentadienide and pentamethylcyclopentadienide (Cp and Cp*), g 6 -arene, and j 3 -HB(pz) 3 The mixed sandwich complexes possess heteroleptic ligand environments which are intermediate between the corresponding metallocenes and hexakis(thioether) complexes, and, accordingly, exhibit structural, spectroscopic, and electrochemical properties which are intermediate between the two types of homoleptic sandwich complexes.…”