Cationic palladium(II)–acetylacetonate complexes containing phosphine and aminophosphine ligands and their catalytic activities in telomerization of 1,3-butadiene with methanol

Novel Route to Cationic Palladium(II)–Cyclopentadienyl Complexes Containing Phosphine Ligands and Their Catalytic Activities

“…The δ values obtained from 1 H and 13 C NMR spectra of compounds 1 – 10 are consistent with NMR data for known palladium complexes with the same phosphine ligands [ 38 , 50 , 51 , 52 , 53 , 54 ]. In each case, the 1 H NMR signal for the cyclopentadienyl group appears as a triplet ( J HP = 2.1–2.3 Hz), due to coupling to the two phosphorus atoms ( Table 2 ).…”

“…The selectivity of the reaction depends on the nature of the nucleophiles and the ligands coordinated to the reactive palladium center ( Scheme 5 ) [ 74 , 75 , 77 , 78 , 79 ]. Previous studies have shown that several palladium complexes with monodentate phosphines[ 51 , 80 , 81 , 82 , 83 , 84 , 85 ], diphosphines [ 86 ], and NHC (NHC—N-heterocyclic carbene) ligands [ 87 , 88 , 89 ] are effective catalysts for the telomerization of BD with methanol.…”

“…Pd(acac) 2 was synthesized according to a procedure from the literature [ 109 ] and recrystallized from acetone. The cationic acetylacetonate complexes were prepared according to known procedures from the literature [ 38 , 50 , 51 , 52 , 53 , 54 ]. All other reagents were obtained commercially and used as received.…”

A Single-Atom Pd Catalyst Anchored on a Porous Organic Polymer for Highly Efficient Telomerization of 1,3-Butadiene with Methanol

“…Homogeneous Pd catalysts in the presence of ligands are found to be extremely reactive for telomerization of 1,3-butadiene with methanol, and ligands play a key role in affecting the reaction activity and selectivity (including chemo- and regioselectivity). Great efforts have been devoted to developing more efficient ligands for substantially improving reaction performance. − Thus far, monodentate phosphines and N-heterocyclic carbenes with varying steric and electronic features are two types of very effective ligands. However, taking into consideration the complicated synthetic procedure, high-cost, and sensitivity of ligands to the reaction conditions, especially with the industrial mixed C4 feed as starting material, the structurally simple and easily available PPh 3 ligand is more appealing, which was chosen as the ligand in the commercial 1,3-butadiene telomerization process for 1-octene production by the Dow Chemical Company in 2007. , Nonetheless, the difficulty of separation and recycling of expensive Pd catalysts from the products is a long-standing challenge in homogeneous catalysis.…”

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

“…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). Sixteen new compounds were fully characterized, and crystal structures of [diμ-(2,10-dimethyl-6-oxa-3,9-dithiaundecane-κ 2 S,S 0 )-bis [trans-dichloropalladium (II)] and (acetylacetonateκ 2 O,O 0 )(2,10-dimethyl-6-oxa-3,9-dithiaundecane-κ 2 S,S 0 ) palladium (II) tetrafluoroborate were determined by X-ray diffraction.…”