15617-18-2Relevant articles and documents
Preparation method of bis (cyanobenzene) palladium dichloride
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Paragraph 0011-0017, (2021/04/03)
The invention discloses a preparation method of bis (cyanobenzene) palladium dichloride, which comprises the following steps: (1) dissolving palladium powder in aqua regia to prepare a palladium active group, cooling, and mixing with benzonitrile; (2) distilling to remove moisture, heating to react, and carrying out hot filtration; and (3) cooling the filtrate, adding the cooled filtrate into an organic solvent, separating out a solid, filtering, washing the obtained filter cake with the organic solvent, and carrying out vacuum drying. According to the method provided by the invention, palladium powder is used as a raw material to replace palladium chloride in the prior art, so that the reaction cost is reduced, and the prepared product is high in purity and high in yield.
Palladium(II)-pivaloyl thiourea complexes: Synthesis, characterisation and their catalytic activity in mild Sonogashira cross-coupling reaction
Khairul, Wan M.,Wahab, Falynee Faha Abdul,Soh, Siti Kamilah Che,Shamsuddin, Mustaffa,Daud, Adibah Izzati
, (2020/08/13)
We report herein the synthesis of Pd(II) complexes featuring pivaloylthiourea derivatives to investigate their catalytic behaviour in Sonogashira cross-coupling reactions as the homogenous catalyst. The SN2 reactions have resulted in pivaloyl thiourea derivatives ligands with general formula (CH3)3C(O)NHC(S)NHR introducing different substituent groups of NO2 (L1), OCH3 (L2), and H (L3) prior to form complexation with Pd(II) (MC1, MC2, and MC3 respectively). All synthesised compounds were characterised via typical selected spectroscopic and analytical methods. Hence, catalytic screening activity revealed that Pd(II)-pivaloyl thiourea catalysed, featuring MC3, is the best catalyst as it gave a high conversion rate up to 99%.
Synthesis of a Bolm's 2,2′-Bipyridine Ligand Analogue and Its Applications
Bedná?ová, Eva,Dra?ínsky, Martin,Malatinec, ?tefan,Císa?ová, Ivana,Lamaty, Frédéric,Kotora, Martin
supporting information, p. 2869 - 2878 (2018/08/17)
A new method of synthesis of an analogue of Bolm's 2,2′-bipyridine ligand based on the catalytic [2+2+2] cyclotrimerization of 1-halodiynes with nitriles was developed. Crucial step of the whole synthesis turned out to be homodimerization of a substituted 2-bromopyridine to the corresponding bipyridine, that was studied and optimized. The newly prepared bipyridine (S,S)-2 was then tested as a chiral ligand in metal-catalyzed enantioselective reactions. Out of the studied reactions the most promising results were obtained in epoxide ring opening (82% yield, 98% ee) and Mukaiyama aldol reaction (>96% yield, 99/1 dr, 92% ee). In the case of Mukaiyama-aldol reaction as well as in the Michael addition, novel ligand 2 proved its robustness compared to Bolm's ligand as it was less sensitive to the purity of used reagents. (Figure presented.).
Pt(II) and Pd(II)-assisted coupling of nitriles and 1,3-diiminoisoindoline: Synthesis and luminescence properties of (1,3,5,7,9-pentaazanona-1,3,6,8-tetraenato)Pt(II) and Pd(II) complexes
Lasri, Jamal,Pedras, Bruno,Haukka, Matti,Berberan-Santos, Mário N.
, p. 195 - 202 (2017/06/13)
Treatment of trans-[PtCl2(NCR)2] 1 (R?=?Me (1a), Et (1b), o-ClC6H4 (1c), p-ClC6H4 (1d), p-(HC[dbnd]O)C6H4 (1e), p-O2NC6H4CH2 (1f)) with 1,3-diiminoisoindoline HN[dbnd]CC6H4C(NH)[dbnd]NH 2 gives access to the corresponding (1,3,5,7,9-pentaazanona-1,3,6,8-tetraenato)Pt(II) complexes [PtCl{NH[dbnd]C(R)N[dbnd]C(C6H4)NC[dbnd]NC(R)[dbnd]NH}] 3a–f, in good yields (65–70%). The reaction of trans-[PdCl2(NCMe)2] 4a with 2 furnishes (1,3,5,7,9-pentaazanona-1,3,6,8-tetraenato)Pd(II) complex [PdCl{NH[dbnd]C(Me)N[dbnd]C(C6H4)NC[dbnd]NC(Me)[dbnd]NH}] 5a, in good yield (65%). However, the reaction of trans-[PdCl2(NCR)2] 4 (R?=?Ph (4b), p-MeC6H4CH2 (4c), p-(HC[dbnd]O)C6H4 (4d), p-O2NC6H4CH2 (4e)) with 2 gives a number of unidentified products. The compounds 3a–f and 5a were characterized by IR,1H,13C and DEPT-135 NMR spectroscopies, elemental analyses and, in the case of the Pt(II) complex [PtCl{NH[dbnd]C(Me)N[dbnd]C(C6H4)NC[dbnd]NC(Me)[dbnd]NH}] 3a, also by X-ray diffraction analysis. Compounds 3a and 3b were also characterized by UV–Vis absorption and luminescence emission spectroscopies. Emission quantum yields of ca. 3?×?10?3 were obtained in dichloromethane solution, and luminescence lifetimes are in the order of the tens of nanoseconds. Both compounds also exhibited luminescence in solid state (polystyrene matrix), with luminescence lifetimes in the order of hundreds of nanoseconds.
Preparation and application of coconut shell activated carbon immobilized palladium complexes
Zhang, Yulian,Xiang, Shuanglong,Wang, Guoqing,Jiang, Hong,Xiong, Chunrong
, p. 1055 - 1063 (2014/04/03)
Coconut shell activated carbon (CSAC) granules were used as carriers to immobilize palladium complexes. Boehm titration showed that the hydroxyl content of the carbon surface reached 0.376 mmol g-1 after 20% HNO 3 treatment. Ethylenediamine, benzyl malononitrile and propyl malononitrile were successfully grafted onto the oxidized CSAC. The bidentate nitrogen ligands complexed Pd2+ samples were characterized by FT-IR, XPS, ICP and N2 adsorption-desorption. In oxidative carbonylation of phenol, three bidentate ligand grafted catalysts were evaluated in a high pressure reaction vessel. The results showed that the ethylenediamine grafted catalyst had a phenol conversion of 12.06% and a diphenyl carbonate (DPC) selectivity of 91.03%. In comparison, the benzyl malononitrile grafted catalyst displayed a phenol conversion of 12.00% and a DPC selectivity of 90.65%. The propyl malononitrile grafted catalyst displayed a phenol conversion of 6.22% and a DPC selectivity of 81.02%. Additionally, the ethylenediamine and the benzyl malononitrile grafted catalysts were also investigated in a continuous packed-bed reactor. The results showed that the phenol conversion and the DPC selectivity were comparative to those obtained in a high pressure reaction vessel. This journal is the Partner Organisations 2014.
Synthesis and properties of new phosphorescent red light-excitable platinum(II) and palladium(II) complexes with schiff bases for oxygen sensing and triplet-triplet annihilation-based upconversion
Borisov, Sergey M.,Saf, Robert,Fischer, Roland,Klimant, Ingo
, p. 1206 - 1216 (2013/04/10)
New Pt(II) and Pd(II) complexes with donor-acceptor Schiff bases are conveniently prepared in only two steps. The complexes efficiently absorb in the red part of the spectrum (ε > 105 M-1 cm -1) and show moderate to strong
Soluble polysiloxane-supported palladium catalysts for the Mizoroki-Heck reaction
Cypryk, Marek,Pospiech, Piotr,Strzelec, Krzysztof,Wasikowska, Karolina,Sobczak, Janusz W.
, p. 30 - 38 (2010/06/20)
Soluble polysiloxanes of various architectures (linear, star-shaped and hyperbranched), having vinyl, 2-butylthioethyl and 2-diphenylphosphinoethyl side groups have been used as supports for palladium(II) catalysts. Catalytic activity of such immobilized palladium complexes was tested in model Mizoroki-Heck reactions. The activity of the complexes in terms of yield and turnover number was comparable to that of PdCl2(PhCN)2. Polysiloxane-supported catalysts show good stability and can be reused several times. Catalysts immobilized on linear polymers show generally better stability than those immobilized on branched structures. Mercury poisoning test indicated that the true catalytic species is the supported complex. According to XPS analysis, palladium in the complexes with polysiloxanes is present as Pd(II). XRF shows however a significant metal leaching after 5-10 reaction cycles.
Studies of thermal decomposition of palladium(II) complexes with olefin ligands
Sz?yk,Barwio?ek
, p. 85 - 89 (2010/01/06)
PdCl2(VTMS)2 (1), PdCl2(PTMSA)2 (2), PdCl2(DMB)2 (3) and PdCl2(DADMS)2 (4), where VTMS-trimethyl(vinyl)silane, DADMS-diallyldimethylsilane, PTMSA-1-phenyl-2
Palladium catalysed alkyne hydrogenation and oligomerisation: A parahydrogen based NMR investigation
Lopez-Serrano, Joaquin,Duckett, Simon B.,Dunne, John P.,Godard, Cyril,Whitwood, Adrian C.
, p. 4270 - 4281 (2009/02/03)
The role phosphine ligands play in the palladium(ii)-bis-phosphine-hydride cation catalysed hydrogenation of diphenylacetylene is explored through a PHIP (parahydrogen induced polarization) NMR study. The precursors Pd(LL′)(OTf)2 (1a-e) [LL′ = dcpe (PCy2CH 2CH2PCy2), dppe, dppm, dppp, cppe (PCy 2CH2CH2PPh2)] are used. Alkyl palladium intermediates of the type [Pd(LL′)(CHPhCH2Ph)](OTf) (2 and 3) are detected and demonstrated to play an active role in hydrogenation catalysis. Magnetization transfer experiments reveal chemical exchange from the α-H of the alkyl ligand of 2a (LL′ = dcpe) and linkage isomer 2e′ (LL′ = cppe) into trans-stilbene on the NMR timescale. Activation parameters (ΔH≠ and ΔS≠) for this transformation have been determined. These experiments, coupled with GC/MS data, indicate that the catalytic activity is greater in methanol, where it follows the order: dcpe > cppe > dppp > dppe > dppm, than in CD 2Cl2. All five of the phosphine systems described are less active than those based on bcope [where bcope is (C8H 14)PCH2-CH2P(C8H14)] and tbucope [where tbucope is (C8H 14)PC6H4CH2P(tBu) 2]. cis, cis-1,2,3,4-Tetraphenyl-buta-1,3-diene is detected as a minor reaction product with Pd(LL′)(PhCH-CHPh-CPh=CHPh)+ (4) also being shown to play a role in the alkyne dimerisation step.
1,1-Ethylenedithiolato complexes of palladium(II) and platinum(II) with isocyanide and carbene ligands
Vicente, Jose,Chicote, Maria Teresa,Huertas, Sonia,Jones, Peter G.
, p. 4268 - 4274 (2008/10/08)
The reactions of [Tl2{S2C=C{C(O)Me}2}]n with [MCl2(NCPh)2] and CNR (1:1:2) give complexes [M{η2-S2C= C{C(O)Me}2}(CNR)2] [R = tBu, M = Pd (1a), Pt (1b); R = C6H3Me2-2,6 (Xy), M = Pd (2a), Pt (2b)]. Compound 1b reacts with AgClO4 (1:1) to give [{Pt(CNtBu)2}2Ag2 {μ2,η2-(S,S′)-{S2C=C{C(O) Me}2}2}](ClO4)2 (3). The reactions of 1 or 2 with diethylamine give mixed isocyanide carbene complexes [M{η2-S2C=C{C(O)Me}2}(CNR)-{C (NEt2)(NHR)}] [R = tBu, M = Pd (4a), Pt (4b); R = Xy, M = Pd (5a), Pt (5b)] regardless of the molar ratic of the reagents. The same complexes react with an excess of ammonia to give [M{η2-(S,S′)-S2C=C{C(O)Me}2}- (CNtBu){C(NH2)(NHtBu)}] [M = Pd (6a), Pt (6b)] or [M{η2-(S,S′)-S2C=C{C(O)Me}2}{C (NH2)(NHXy)}2] [M = Pd (7a), Pt (7b)] probably depending on steric factors. The crystal structures of 2b, 4a, and 4b have been determined. Compounds 4a and 4b are isostructural. They all display distorted square planar metal environments and chelating planar E,Z-2,2-diacetyl-1,1-ethylenedithiolato ligands that coordinate through the sulfur atoms.
