Tag: 500-600

Application In Synthesis of Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)On October 14, 2019 ,《Synthesis, Structures, and Norbornene Polymerization Behavior of Imidazo[1,5-a]pyridine-sulfonate-Ligated Palladacycles》 was published in Organometallics. The article was written by Dong, Jie; Li, Minliang; Wang, Baiquan. The article contains the following contents:

Two imidazo[1,5-a]pyridine-sulfonate proligands, L1 and L2, were synthesized in five-step reactions. Treatment of the proligands with palladacycles {[Pd(OAc)(8-Me-quin-H)]2, [Pd(dmba)(μ-Cl)]2, and [Pd(o-acetanilido)(μ-trifluoroacetato)]2} yielded the desired five-membered C(sp3),N-chelated (Pd1, Pd2), C(sp2),N-chelated (Pd3, Pd4), and six-membered C(sp2),O-chelated (Pd5, Pd6) palladacycles, resp. All these complexes were fully characterized by 1H and 13C NMR, IR, high-resolution mass spectrometry, and elemental anal. The mol. structures of complexes Pd1, Pd2, Pd4, and Pd5 were determined by single-crystal x-ray diffraction anal. In the presence of MAO or Et2AlCl, Pd1-Pd6 exhibited activities toward the addition polymerization of norbornene which decreased in the order Pd6 > Pd5 > Pd4 > Pd2 > Pd3 > Pd1. The Pd1-Pd6/MAO catalytic system showed high thermal stability and reached the highest activity at 100° (6.0 × 107 g of PNB (mol of Pd)-1 h-1 with 99.9% conversion). In the presence of Et2AlCl with low loading (100 equiv), Pd5 and Pd6 exhibited high activities (up to 2.9 × 107 g of PNB (mol of Pd)-1 h-1 with 96.5% conversion). It was demonstrated that the structures of palladacycles and the substituents on the ligands significantly affected the activities of these complexes. In the experimental materials used by the author, we found Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)(cas: 18987-59-2Application In Synthesis of Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II))

Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)(cas: 18987-59-2) belongs to organochlorine compounds. The wide structural variety and divergent chemical properties of organochlorides lead to a broad range of names, applications, and properties.Application In Synthesis of Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II) Organochlorine compounds have wide use in many applications, though some are of profound environmental concern, with TCDD being one of the most notorious.

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

The author of 《Pd/Xiang-Phos-catalyzed enantioselective intermolecular carboheterofunctionalization under mild conditions》 were Tao, Mengna; Tu, Youshao; Liu, Yu; Wu, Haihong; Liu, Lu; Zhang, Junliang. And the article was published in Chemical Science in 2020. Synthetic Route of C18H24Cl2N2Pd2 The author mentioned the following in the article:

A mild and practical Pd/Xiang-Phos-catalyzed enantioselective intermol. carboheterofunctionalization reaction of 2,3-dihydrofurans I (R = H, 4-MeC6H4, quinolin-2-yl, benzofuran-5-yl, 4-MeO2CC6H4) was developed, leading to various optically active fused furoindolines II (R1 = H, F, Me, R2 = H, Cl, Me, CF3, etc., R3 = H, F, MeO2C, Me, etc., R4 = H, F, R1R2 = -N=CHCH=N-, PG = Ts, SO2Ph), III (R = 4-MeC6H4, 4-MeO2CC6H4, benzofuran-5-yl), and tetrahydrofurobenzofurans IV (R5 = H, F, Me, OMe, R6 = H, F, Me, R7 = H, F, OMe) and V (R = 4-MeC6H4, 4-MeO2C6H4, benzofuran-5-yl, quinolin-2-yl, H). The key to this transformation is employing two newly modified N-Me-Xiang-Phos ligands (S,RS)-VI (Ar = Ph, 3,5-(tert-Bu)2-4-MeOC6H2) as chiral ligands under mild conditions. Moreover, this synthetic methodol. can be efficiently applied to a variety of complex polysubstituted heterocycles with high chemo-, regio-, and enantio-selectivities via introducing diverse substituents on furan rings, which were hard to access by other routes. After reading the article, we found that the author used Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)(cas: 18987-59-2Synthetic Route of C18H24Cl2N2Pd2)

Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)(cas: 18987-59-2) belongs to organochlorine compounds. Many organochlorine compounds have been isolated from natural sources ranging from bacteria to humans. Chlorinated organic compounds are found in nearly every class of biomolecules and natural products including alkaloids, terpenes, amino acids, flavonoids, steroids, and fatty acids. Synthetic Route of C18H24Cl2N2Pd2

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

《Versatile coordination and C-H activation of a multi-donor phosphinoferrocene carboxamide ligand in Pd(II) complexes》 was written by Horky, Filip; Skoch, Karel; Cisarova, Ivana; Stepnicka, Petr. Safety of Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II) And the article was included in Dalton Transactions in 2019. The article conveys some information:

A multi-donor phosphinoferrocene carboxamide, FcCONHCH2CH2PPh2 (1, Fc = ferrocenyl), was prepared, converted into the corresponding phosphine oxide 1O and phosphine selenide 1Se and, mainly, studied as a ligand in Pd(II) complexes. In its native form, amide 1 preferentially coordinated soft Pd(II) as a simple phosphine, giving rise to mixtures of cis and trans-[PdX2(1-κP)2] (2; X = Cl (a), Br (b), and I (c)), wherein the isomer ratios depended on the auxiliary halide ligand or, alternatively, to the complex [(LNC)PdCl(1-κP)] (6, LNC = 2-[(dimethylamino)methyl-κN]phenyl-κC1). This coordination mode was nevertheless easily changed when creating a vacant coordination site at the palladium. Thus, treatment of 2a with NH4[PF6] in the presence of free 1 produced [PdCl(1-κP)3][PF6] (3), while complete halogen removal with a Ag(I) salt led to cationic complexes cis-[Pd(1-κ2O,P)2]X2 (4, X = CF3SO3 (a), ClO4 (b), BF4 (c)) or [(LNC)Pd(1-κ2O,P)]X (7a and 7b), containing seven-membered O,P-chelate rings. In contrast, amide nitrogen deprotonation with KOt-Bu followed by spontaneous intramol. halogen substitution resulted in the transformation of 6 into the chelate complex [(LNC)Pd{(1 – H)-κ2N,P}] (8) featuring a five-membered N,P-chelate ring, and in the conversion of 2a and 2b into the product of C-H bond activation [Pd{Fe(η5-C5H3CONCH2CH2PPh2-κ3C,N,P)(η5-C5H5)}(1-κP)] (5), with doubly chelating deprotonated 1. Importantly, complexes 2-4-5 and 6-7-8 were mutually interconverted in triads (by protonation/deprotonation and by halide addition/abstraction), which highlights the flexible coordination and chem. stability of ligand 1. The crystal structures of 1O·1/2H2O, trans-2a·MeCN, trans-2b·3C2H4Cl2, trans-2c·2.5C2H4Cl2, 4a·CH2Cl2, 5·3CHCl3·Et2O, and 8 were determined by single-crystal X-ray diffraction anal., and the representative compounds were studied by cyclic voltammetry. The results came from multiple reactions, including the reaction of Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)(cas: 18987-59-2Safety of Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II))

Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)(cas: 18987-59-2) belongs to organochlorine compounds. Many organochlorine compounds have been isolated from natural sources ranging from bacteria to humans. Safety of Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II) Chlorinated organic compounds are found in nearly every class of biomolecules and natural products including alkaloids, terpenes, amino acids, flavonoids, steroids, and fatty acids.

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Kukowski, Jonathan E.; Smoliakova, Irina P. published an article on February 1 ,2019. The article was titled 《Steric and electronic effect of secondary phosphines in reactions with cyclopalladated complexes》, and you may find the article in Polyhedron.Name: Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II) The information in the text is summarized as follows:

Reactions of secondary phosphines HPR2 (b-e; R = 4-MeOC6H4, 4-CF3C6H4, mesityl, 1-adamantyl) and HPPhtBu (f) with cyclopalladated complexes (CPCs) derived from N,N-dimethylbenzylamine (1), L-fenchone methyloxime (FenchOx, 3), (S)-N,N-dimethylbenzylamine (9), and (S)-di-2,4-tert-butyloxazoline (11) were studied. Phosphination of the cyclopalladated ligands in complexes 1 and 3 was observed using either 4.5:1 or 9:1 molar ratios of HPAr2 (b,c) to CPC in the presence of 9 equiv of Cs2CO3. The corresponding N,P-ligands (2b,c, 4b,c) were isolated in 44-59% yields. Reactions of the sterically hindered HPMes2 with CPCs 1 and 3 provided the phosphine oxide (4d’), only for the latter complex (32% yield). Attempts to synthesize N,P ligands with HPAd2 were unsuccessful with either palladacycle. Major products of the reactions of complexes 1 and 3 with bulky HPMes2 and HPAd2 were either rare mononuclear complexes [(1,2-Me2NCH2C6H4)Pd(HPR2)Cl] (5d,e; up to 90%) and [(FenchOx)Pd(HPR2)Cl] (7d,e; 81 and 86%) with an ancillary secondary phosphine ligand or dinuclear monophosphido, monochloro-bridged complexes [(1,2-Me2NCH2C6H4)2Pd2(μ-PR2)(μ-Cl)] (6d, 98%) and [(FenchOx)2Pd2(μ-PR2)(μ-Cl)] (8d,e, 69% and 66%) depending on the HPR2/CPC molar ratio used. Enantiopure CPC 3 reacted with racemic HPPhtBu to give a single diastereomer of the phosphination product (4f, 12% yield). Attempts to use the racemic phosphine in transformations with two other enantiopure CPCs, to form a C-PPhtBu bond were unsuccessful. Instead, reactions of these two complexes with racemic HPPhtBu provided monophosphido, monochloro-bridged CPCs in 32 and 76% yield, resp. Anal. of 1H, 13C{1H} and 31P{1H} NMR data of all new Pd(II) complexes and N,P ligands is provided. An x-ray crystallog. study of complex 7d proved its trans-N,P geometry.Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)(cas: 18987-59-2Name: Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)) was used in this study.

Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)(cas: 18987-59-2) belongs to organochlorine compounds. Many organochlorine compounds have been isolated from natural sources ranging from bacteria to humans. Chlorinated organic compounds are found in nearly every class of biomolecules and natural products including alkaloids, terpenes, amino acids, flavonoids, steroids, and fatty acids. Name: Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Quality Control of Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)On May 13, 2019 ,《Synthesis and Catalytic Applications of Heterobimetallic Carbene Complexes Obtained via Sequential Metalation of Two Bisazolium Salts》 appeared in Organometallics. The author of the article were Boehmer, Maximilian; Guisado-Barrios, Gregorio; Kampert, Florian; Roelfes, Florian; Tan, Tristan Tsai Yuan; Peris, Eduardo; Hahn, F. Ekkehardt. The article conveys some information:

A simple sequential metalation approach starting from the imidazolium/benzimidazolium salt 4(I)2 yielded the heterobimetallic RhIII/M (M = PdII, IrI, AuI, RuII) complexes [6]-[9]. Alternatively, a sym. 1,3-imidazolium substituted benzene was used for the preparation of the heterobimetallic M’/PdII (M’ = RhIII, IrIII) complexes [12] and [13]. The versatile stepwise approach used for the preparation of complexes [6]-[9] involved the deprotonation reaction of the bisazolium salt 4(I)2 in the presence of [RhCp*(Cl)2]2 to afford the monometallic complex [5]I featuring a chelating coordinated bidentate CNHC^Cphenyl ligand. Complex [5]I was reacted with Ag2O to give a nonisolated RhIII/AgI complex which in a subsequent transmetalation reaction yielded the heterobimetallic RhIII/M bis-NHC complexes (M = PdII [6], IrI [7], AuI [8], RuII [9]). Similarly, heterobimetallic M’/PdII bis-NHC complexes [12] (M’ = RhIII) and [13] (M’ = IrIII) have been prepared from a sym. bisazolium salt by generating first the monometallic M’ complexes followed by a transmetalation reaction of the in situ generated M’/AgI complexes with [Pd(dmba)(μ-Cl)]2. The RhIII/PdII complexes [6] and [12] and the IrIII/PdII complex [13] were used as catalysts for two orthogonal tandem reactions, namely, the Suzuki-Miyaura coupling/transfer hydrogenation and the Suzuki-Miyaura-coupling/α-alkylation of ketones. The catalytic activity of the heterobimetallic complexes was compared to mixtures of the related monometallic analogs [14]-[17], with the heterobimetallic complexes generally showing a higher catalytic activity. In addition, nBuOH was found to play a dual role as an alkylating and reducing agent in the Suzuki-Miyaura coupling/α-alkylation of ketones. After reading the article, we found that the author used Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)(cas: 18987-59-2Quality Control of Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II))

Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)(cas: 18987-59-2) belongs to organochlorine compounds. Alkanes and aryl alkanes may be chlorinated under free radical conditions, with UV light. However, the extent of chlorination is difficult to control. Aryl chlorides may be prepared by the Friedel-Crafts halogenation, using chlorine and a Lewis acid catalyst.Quality Control of Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

《Synthesis, Characterization and Theoretical Investigation on Thiazoline-Derived Palladium-Complexes-Catalyzed Denitrogenative Cross-Coupling of Aryl Halides with Arylhydrazines》 was published in ChemistrySelect in 2019. These research results belong to Sudharsan, Murugesan; Thirumoorthy, Krishnan; Nethaji, Munirathinam; Suresh, Devarajan. Quality Control of Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II) The article mentions the following:

Homo- and heteroleptic palladium(II) complexes I, II and III [R = H, Me] of thiazoline derived ligand were synthesized and their catalytic application was reported. The reactions of 2-(4,5-dihydro-2-thiazolyl)phenol with PdCl2 and [(1-(CH3)2NCH2C6H4)PdCl]2 in 2:1 molar ratios afforded the homoleptic palladium complex, I and the heteroleptic palladium complex II resp. Equimolar reactions of 2-(4,5-dihydro-2-thiazolyl)phenol with PdCl2 and 8-quinolinol or 2-methyl-8-quinolinol under reflux condition produced the heteroleptic palladium complexes III [R = H, Me] in good yields. The mol. structures of ligand and palladium complexes I, II, III were confirmed through multinuclear NMR spectroscopic techniques and further the crystal structure for palladium complexes I and II were established. Under the optimized reaction condition, the heteroleptic palladium complex II displayed an excellent catalytic activity with a maximum turn over frequency of 49.5 h-1 for the conversion of biaryls from aryl halides and unactivated phenylhydrazine. The energies, activation barriers and transition state structures of reaction involved in the catalytic cycle were assessed by utilizing quantum chem. method to confirm Csp2-Csp2 bond formation reaction catalyzed by heteroleptic palladium complex II. The results came from multiple reactions, including the reaction of Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)(cas: 18987-59-2Quality Control of Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II))

Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)(cas: 18987-59-2) belongs to organochlorine compounds. Alkanes and aryl alkanes may be chlorinated under free radical conditions, with UV light. Quality Control of Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II) However, the extent of chlorination is difficult to control. Aryl chlorides may be prepared by the Friedel-Crafts halogenation, using chlorine and a Lewis acid catalyst.

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

《Synthesis and characterization of palladium(II) complexes with hybrid phosphinoferrocene ligands bearing additional O-donor substituents》 was written by Vosahlo, Petr; Schulz, Jiri; Skoch, Karel; Cisarova, Ivana; Stepnicka, Petr. Name: Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II) And the article was included in New Journal of Chemistry in 2019. The article conveys some information:

While 1,1′-bis(diphenylphosphino)ferrocene (dppf) is widely used as a ligand in coordination chem. and catalysis, its congeners with oxygen-containing functional groups have long been overlooked. Accordingly, we studied the coordination behavior in Pd(II) complexes of three phosphinoferrocene ligands bearing secondary O-donor groups, Ph2PfcR, wherein R = CHO (1), Ac (2) and CMe2(OH) (3), and fc = ferrocene-1,1′-diyl. Depending on the stoichiometry, reactions of 1-3 (L) with [PdCl2(cod)] (cod = η2:η2-cycloocta-1,5-diene) produced the resp. mono- and dipalladium complexes, trans-[PdCl2(L-κP)2] and trans-[PdCl(μ-Cl)(L-κP)]2. Compound [PdCl(μ-Cl)(3-κP)]2 was found to dehydrate readily, giving rise to [PdCl(μ-Cl)(Ph2PfcC(Me):CH2-κP)]2. Furthermore, ligands 1-3 cleaved [(LNC)Pd(μ-Cl)]2 (LNC = 2-((dimethylamino-κN)methyl)phenyl-κC1), yielding [(LNC)PdCl(L-κP)], which were converted into the cationic complexes [(LNC)PdCl(L)]X (L/X = 1/PF6, 2/SbF6, 3/PF6). Compounds with ligands 1 and 2 were structurally authenticated as stable bis-chelate complexes. In contrast, the product featuring ligand 3 was rather unstable and converted into [(LNC)Pd(AcOEt-κO)(3-κP)][PF6] upon recrystallization Weak oxygen coordination was confirmed via reactions of [(LNC)PdCl(L)]X with (PhCH2NEt3)Cl in which the parent chloride complexes were regenerated, and this was further corroborated by DFT computations. Our findings, pointing to hemilabile coordination of 1-3, are relevant for catalysis because de-coordination of the weaker binding O-donor moiety may open a vacant site for a substrate, thereby enhancing the catalytic properties of metal complexes with ligands of this type. In the experiment, the researchers used Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)(cas: 18987-59-2Name: Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II))

Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)(cas: 18987-59-2) belongs to organochlorine compounds. The wide structural variety and divergent chemical properties of organochlorides lead to a broad range of names, applications, and properties. Aliphatic organochlorides are often alkylating agents as chlorine can act as a leaving group, which can result in cellular damage.Name: Di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II)

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics