[Pd(acac)(MeCN)₂]BF₄: air-tolerant, activator-free catalyst for alkene dimerization and polymerization

Abstract

[Pd(acac)(MeCN)2]BF4 has been observed to catalyze selective substituted styrene dimerization and addition norbornene polymerization.

Addition copolymerization of norbornene lactone catalyzed by Pd complexes

“…Chlorobenzene was purified by distillation from CaH 2 before use. Pd(allyl)IDippCl 25 (IDipp = 1,3‐bis[2,6‐diisopropylphenyl]imidazolin‐2‐ylidene)), Pd(acac)(MeCN) 2 BF 4, 26 endo ‐5‐norbornene‐2‐carboxylic acid methyl ester ( endo ‐NBCO 2 Me), 27,28 endo ‐3‐methyl‐5‐norbornene‐2‐carboxylic acid methyl ester ( endo ‐NB(Me)CO 2 Me), 28,29 endo ‐ and exo ‐NBLs 24,30 were synthesized according to the literatures.…”

Synthesis of mononuclear and dinuclear palladium (II) complexes containing oxadithioether ligands and their catalytic activities in norbornene polymerization

“…The complexes [Pd(acac)(MeCN) 2 ]BF 4 and Pd(cod)Cl 2 were prepared according to published procedures. [39,40,44] 5-methoxycarbonylnorbornene was synthesized in stainless steel autoclave by the Diels-Alder reactions of dicyclopentadiene with methyl acrylate (t = 180 C, 6 h). The crude products were twice distilled over CaH 2 under argon.…”

“…It is known that aluminum alkyl-free cationic Pd-catalyzed systems with O^O-chelating ligands (O^O = β-diketonates or carboxylates) activated with Lewis acid such as BF 3 ÁOEt 2 have shown promising results for polymerization of norbornene and its derivates. [36,38,39,80,81] The main results are listed in Tables 1 and 2. All 1a-8a complexes produce polynorbornene, showing moderate to high activities on the order of 1.5Á10 5 -1.4Á10 7 g PNB mol Pd À1 h À1 .…”

“…[31][32][33][34][35] However, Pd (II) complexes with bidentate oxadithioether ligands as catalysts for olefin polymerization have only rarely been applied. In previous research, our group reported the synthesis of various cationic acetylacetonate palladium complexes, as well their usage as efficient precursors for the polymerization of norbornene and its derivatives, [36][37][38][39] polymerization of phenylacetylene, [40] selective dimerization or hydroamination of vinylarenes, [39,41] and telomerization of butadiene with methanol. [42] In this report, we describe the results of the synthesis of novel palladium complexes with SOS-type ligands trans-[PdCl 2 (μ-L)] 2 and [Pd(acac)(L)][BF 4 ] (L = RS(CH 2 ) 2 O(CH 2 ) 2 SR, R = Me, Et, n Pr, i Pr, n Bu, i Bu, n-hexyl, benzyl).…”

“…[ 31–35 ] However, Pd (II) complexes with bidentate oxadithioether ligands as catalysts for olefin polymerization have only rarely been applied. In previous research, our group reported the synthesis of various cationic acetylacetonate palladium complexes, as well their usage as efficient precursors for the polymerization of norbornene and its derivatives, [ 36–39 ] polymerization of phenylacetylene, [ 40 ] selective dimerization or hydroamination of vinylarenes, [ 39,41 ] and telomerization of butadiene with methanol. [ 42 ]…”