The dichloromethane solvates of the isomers tetrakis(mu-1,3-benzothiazole-2-thiolato)-kappa(4)N:S;kappa(4)S:N-dipalladium(II)(Pd-Pd), (I), and tetrakis(mu-1,3-benzothiazole-2-thiolato)-kappa(6)N:S;kappa(2)S:N-dipalladium(II)(Pd-Pd), (II), both [Pd2(C7H4NS2)4] x CH2Cl2, have been synthesized in the presence of (o-isopropylphenyl)diphenylphosphane and (o-methylphenyl)diphenylphosphane. Both isomers form a lantern-type structure, where isomer (I) displays a regular and symmetric coordination and isomer (II) an asymmetric and distorted structure. In (I), sitting on an centre of inversion, two 1,3-benzothiazole-2-thiolate units are bonded by a Pd-N bond to one Pd atom and by a Pd-S bond to the other Pd atom, and the other two benzothiazolethiolate units are bonded to the same Pd atoms by, respectively, a Pd-S and a Pd-N bond. In (II), three benzothiazolethiolate units are bonded by a Pd-N bond to one Pd atom and by a Pd-S bond to the other Pd atom, and the fourth benzothiazolethiolate unit is bonded to the same Pd atoms by, respectively, a Pd-S bond and a Pd-N bond.
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http://dx.doi.org/10.1107/S0108270107052353 | DOI Listing |
Org Lett
January 2025
China Guangxi Key Laboratory of Pharmaceutical Precision Detection and Screening, Guangxi Key Laboratory of Bioactive Molecules Research and Evaluation, and Key Laboratory of Micro-Nanoscale Bioanalysis and Drug Screening of Guangxi Education Department, Pharmaceutical College, Guangxi Medical University, Nanning 530021, China.
Herein, a one-pot domino catalyzed three-component process is described, which is initiated by a palladium/zinc cooperatively catalyzed cycloaddition between trimethylenemethane (TMM) and unactivated alkyl/aryl imines, followed by one-pot isomerization and Zn(OTf)-catalyzed DDQ oxidation, furnishing valuable substituted pyrroles. We disclose that the palladium/zinc cooperative catalysis affords a dual-Zn(OTf)-stabilized azapalladacycle, wherein the Pd-N bond is polarized by Zn(OTf), facilitating a unique outer-sphere allylic amination. Moreover, subsequent DDQ dehydrogenation can be feasibly promoted by zinc catalysis.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
School of Chemistry and Chemical Engineering, Nanchang University, No. 999 Xuefu Avenue, Nanchang, 330031, P. R. China.
Developing a method for the tandem hydrogenative hydrogenolysis of bio-based furfuryl aldehydes to methylfurans is crucial for synthesizing sustainable biofuels and chemicals; however, it poses a challenge due to the easy hydrogenation of the C=C bond and difficult cleavage of the C-O bond. Herein, a palladium (Pd) single-atom-supported covalent organic framework was fabricated and showed a unique 2,5-dimethylfuran yield of up to 98.2 % when reacted with 5-methyl furfuryl aldehyde in an unprecedented water solvent at 30 °C.
View Article and Find Full Text PDFDalton Trans
November 2024
Fujian Key Laboratory of Drug Target Discovery and Structural and Functional Research, Higher Educational Key Laboratory for Nano Biomedical Technology of Fujian Province, The School of Pharmacy, Fujian Medical University, Fuzhou, Fujian, 350122, People's Republic of China.
Superatoms are special clusters with similar physicochemical properties to individual atoms in the periodic table, which open up new avenues for exploring inexpensive catalysts. Given that the ZrO superatom possesses the same number of valence electrons as a Pd atom, the mechanisms of the Suzuki-Miyaura reaction catalyzed by (ZrO) ( = 1-4) clusters have been investigated and compared with the corresponding Pd ( = 1-4) species to explore superatom-based catalysts for the formation of C-C bonds a density functional theory (DFT) study. It was interesting to find that the catalytic activities of (ZrO) ( = 1-4) towards the Suzuki-Miyaura reaction gradually improved as the cluster size increased.
View Article and Find Full Text PDFInorg Chem
October 2024
Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing 100084, China.
Thermodynamic studies of transition-metal intermediates are crucial for understanding of metal-catalyzed transformations. Herein, a series of arylpalladium cyanomethanides were synthesized and characterized. Their palladium-carbon bond heterolysis energies (Δ(Pd-C)) were determined in DMSO for the first time by equilibrium methods.
View Article and Find Full Text PDFFam Process
September 2024
Institute of Education and Child Studies, Leiden University, Leiden, The Netherlands.
The disruption of the parent-child attachment bond due to parental death (PD) may lead to lingering feelings of unsafety or insecurity that might potentially transfer to adult intimate relationships. The aim of the current study was to investigate whether experiencing childhood parental death (CPD) was associated with adult romantic relationship formation and stability, attachment style, and relationship satisfaction, and whether this is dependent on (in)secure parental bonding. In this cross-sectional study, relationship indicators were assessed using self-report questionnaires in adults (25-45 years old) who experienced PD during childhood (n = 236), in adulthood (n = 301), and who did not experience PD (n = 278).
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