Unusual Influence of the Structures of Transition Metal Complexes on Catalytic C–S and C–Se Bond Formation Under Homogeneous and Heterogeneous Conditions

Abstract

In the presence of transition metal catalysts, hydrothiolation and hydroselenation reactions, as well as bisthiolation and bisselenation reactions, have been successfully carried out with high selectivities and yields. New transition metal-catalyzed synthetic methods have been developed for the preparation of vinyl sulfides and vinyl selenides of various types. Mechanistic study has revealed that a homogeneous catalytic system based on phosphine complexes of palladium is the

Tiara-like Octanuclear Palladium(II) and Platinum(II) Thiolates and Their Inclusion Complexes with Dihalo- or Iodoalkanes

“…8 Thiolate-bridged polynuclear group 10 transition-metal complexes with chain structures, [M(-SR) 2 ] n (M = Ni, Pd), have been investigated in detail because they provide efficient catalysis of atom-economical organic reactions such as regioselective additions of thiols and disulfides across alkynes. [8][9][10][11][12][13] Tiara-like complexes, which are also polynuclear group 10 transition-metal thiolates and are characterized by toroidal architectures, have been studied extensively, both in terms of their intriguing structural features and with respect to the preparation of monodisperse metal sulfide nanoparticles, 14 non-linear optical materials, 15 photoactive water-reducing catalysts, [16][17] and host-guest chemistry. 15,[18][19][20][21] Tiara-like nickel complexes have received considerable attention resulting in the preparation of complexes with a variety of ring sizes [Ni(-SR) 2 ] n (n = [4][5][6][8][9][10][11][12].…”

“…[8][9][10][11][12][13] Tiara-like complexes, which are also polynuclear group 10 transition-metal thiolates and are characterized by toroidal architectures, have been studied extensively, both in terms of their intriguing structural features and with respect to the preparation of monodisperse metal sulfide nanoparticles, 14 non-linear optical materials, 15 photoactive water-reducing catalysts, [16][17] and host-guest chemistry. 15,[18][19][20][21] Tiara-like nickel complexes have received considerable attention resulting in the preparation of complexes with a variety of ring sizes [Ni(-SR) 2 ] n (n = [4][5][6][8][9][10][11][12]. 15,[17][18][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] In contrast, although several tiara-like hexanuclear palladium complexes have been reported, 9,14,…”

A novel and efficient synthesis of selenides

“…Phenyl bromide could also afford excellent product yield of 92% after a longer reaction time of 6 h, whereas trace amount of product was observed for aryl chloride (Table 3, entries 10 and 11). Phenyl bromides bearing electron-donating groups of Me-and MeO-could finish the reaction in shorter time than the other reactants to produce the corresponding selenides in excellent yields of 96-98% (Table3, entries [12][13][14][15]. The steric hindrance of o-bromotoluene and o-bromo-anisole displayed no effect on yield, but resulted in longer reaction times than their corresponding para-isomers (Table 3, entries 13 and 15).…”

“…Recently, an effective method to synthesize unsymmetrical selenides has been reported through the reaction of organic halides with the product of diselenide reduction. 8 Catalysts like indium, 9 copper, 10 palladium or tin, 11 nickel, 12 ruthenium 13 and…”

The Formation of Csp 2 S and Csp 2 Se Bonds by Substitution and Addition Reactions Catalyzed by Transition Metal Complexes

“…Chemical selectivity is a main concern in the design of cross-coupling reactions in order to improve the ratio of hetero-/homocoupling products and to avoid reduction of the C-halogen bond. However, examination of the addition reactions raised other important problems -stereoselectivity in the case of the addition of dichalcogenides and regioselectivity for the addition of thiols and selenols [99].…”