Polymerization of hydroxyacetylenes by ruthenium alkylidene complexes

Catalytic transformation of phenylacetylene mediated by phosphine-free ruthenium alkylidene complexes

“…On the other hand, second-generation ruthenium alkylidene catalysts have also been reported as initiators mediating the hydrosilylation of alkynes [26], the polymerization of ortosubstituted phenylacetylenes [27], hydroxyacetylenes [28], and 1,6-heptadiynes [29]. Although second-generation phosphine-free ruthenium catalysts have been reported as inactive in the dimerization of silylacetylenes [19], to the best of our knowledge those complexes have not been used as catalysts for the intermolecular cyclotrimerization of 1-alkynes.…”

Synthesis of End‐Functionalized Polyacetylenes that Contain Polar Groups by Employing Well‐Defined Palladium Catalysts

“…Darkwa, Pollack and co-workers have developed well-defined [(diphosphine)Pd-A C H T U N G T R E N N U N G (NCCH 3 )A C H T U N G T R E N N U N G (CH 3 )]OTf-type catalysts and successfully polymerized phenylacetylene (PA) to obtain poly(PA)s with moderate molecular weights in good yields. [36] The incorporation of a methyl group at their chain ends was confirmed by 1 H NMR and 13 C NMR spectroscopic analysis of the synthesized poly(PA)s. This observation indicated that PA was polymerized through a coordination/insertion mechanism.…”

“…Transition-metal catalysts polymerize various acetylene monomers to yield substituted polyacetylenes with useful functions, such as electro-active and photoluminescent properties, as a result of their conjugated main chains, their high gas permeability, and the helix-forming ability of their rigid backbones. [1][2][3][4][5] Well-defined transition-metal catalysts that contain tantalum, [6] molybdenum, [7][8][9] ruthenium, [10][11][12][13][14] rhodium, [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31] nickel, [32] and palladium [33][34][35][36][37][38][39][40] are especially useful for acetylene polymerization, because they allow control over catalytic activity by judicious ligand design, thereby enabling living/controlled polymerization. As a result, precise modification of the polymer architectures are achieved, which enable the synthesis of block copolymers and starshaped polymers.…”

Carbonyl Complexes of Molybdenum and their Catalytic Activity

“…Recent studies on polymerization reaction have revealed that the molybdenum(II) complex [MoCl(SnCl 3 )(CO) 3 (NCMe) 2 ] (2) initiates the polymerization of hydroxyacetylenes, such as 3-butyn-2-ol and 2-methyl-3-butyn-2-ol, in a similar way as alkylidene complexes of ruthenium [56].…”

“…Carbonyl complexes of molybdenum are of great utility owing to their applications as precursors for the generation of true catalysts for such reactions as metathesis , metathesis polymerization and oligomerization [39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][54][55][56], radical reactions [57][58][59][60][61][62][63][64][65], hydrogenation [66][67][68][69][70][71][72][73][74], hydrosilylation [75][76][77][78][79], hydrogermylation [80,81], hydrostannation [82][83][84][85][86][87]…”