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卷 45, 编号 4 (2019)
- 年: 2019
- 文章: 6
- URL: https://journals.rcsi.science/1070-3284/issue/view/13362
Article
The First Heterometallic Acetate-Bridged Pt(II)–Pd(II) Complex: Synthesis, Structure, and Formation of Bimetallic PtPd2 Nanoparticles
摘要
The reaction of platinum acetate blue, empirically described as Pt(OOCMe)2.50, with palladium(II) acetate Pd3(μ-OOCMe)6 gave the first heterometallic acetate-bridged platinum(II) and palladium(II) complex Pd2Pt(μ-OOCMe)6 (I) as co-crystallizates 17Pd2Pt(μ-OOCMe)6 ⋅ 4Pd3(μ-OOCMe)6 ⋅ 42C6H6 (IIa) and 17Pd2Pt(μ-OOCMe)6 ⋅ 4 Pd3(μ-OOCMe)6 (IIb). Single crystal X-ray diffraction (CIF files CCDC nos. 1568105 and 1852744), EXAFS, and quantum chemical studies (DFT and QTAIM) of complex I revealed a slightly distorted triangular structure similar to the structure of palladium(II) acetate Pd3(μ-OOCMe)6 and hypothetical platinum(II) complex Pt3(μ-OOCMe)6. The thermal decomposition of complex IIa gives the bimetallic alloy PtPd2. A combined X-ray diffraction and EXAFS study demonstrated that the obtained material consists of core (Pt)–shell (Pd) particles with an average size of ~28 nm and a minor amount of smaller (~5 nm) PdO nanoparticles on the surface. The obtained results are useful for the understanding of the nature and structure of the supported phase of heterogeneous Pt–Pd catalysts.
253-265
Hydrogenation of C=C and C=N Bonds of the Amide-Imine Ligand in the Metal Coordination Sphere in the Reaction of Yttrium Bis(alkyl) Complex [2,6-iso-Pr2C6H3NC(=CH2)C(Me)=NC6H3-iso-Pr2-2,6]Y(CH2SiMe3)2(THF) with Molecular Hydrogen
摘要
On treatment of the yttrium bis(alkyl) complex [ArNC(=CH2)C(Me)=NAr]Y(CH2SiMe3)2(THF) (I, Ar = C6H3-iso-Pr2-2.6) containing an amide-imine ligand, with molecular hydrogen, hydrogenation of the C=N and C=C bonds takes place along with hydrogenolysis of Y−C bonds. The reaction is also accompanied by redistribution of nitrogen ligands and results in the formation of the yttrium complexes [ArNCH(Me)CH(Me)NAr]Y[ArN(=CH2)CH(Me)N(H)Ar](THF) (IIMeMe) and [ArNCH(Me)-C(=CH2)NAr]Y[ArN(=CH2)CH(Me)N(H)Ar](THF) containing, the monoanionic ene-amide-amine moiety [ArNC(=CH2)CH(Me)N(H)Ar]−, together with the dianionic diamide ligands [ArNCH(Me)CH(Me)NAr]2− or [ArNCH(Me)C(=CH2)NAr]2− (CIF file CCDC no. 1873206).
266-272
Atmospheric Oxygen Influence on the Chemical Transformations of 4,5-Dimethyl-1,2-Phenylenediamine in the Reactions with Copper(II) Pivalate
摘要
The one-pot synthesis of the Cu(II) complex with hard to access symmetric bis-azoligand is carried out by the reaction of 4,5-dimethyl-1,2-phenylenediamine (Dmpda) with the [Cu2(Piv)4(HPiv)2] complex (Piv is the pivalate anion) in the presence of atmospheric oxygen. The amine form of the ligand takes place and the bis-diiminosemiquinone biradical redox form of the ligand does not take place in the [CuLazo] complex as unambiguously shown by the data of X-ray structure analysis (CIF files CCDC nos. 1877582 (I · DMF) and 1877583 (II), ESR spectroscopy, SQUID magnetometry, and electrochemical and quantum chemical studies. The coordination polymer [Cu2(Piv)4(Dmpda)]n in which the Dmpda molecules perform the bridging function is formed in the same reaction mixture under reduced air pressure.
273-287
Synthesis of New Bulky Bis(amidine) with the Conformationally Rigid meta-Phenylene Bridge and Its Dilithium Derivative [1,3-C6H4{NC(Ph)N(2,6-iso-Pr2C6H3)}2]Li2(TMEDA)2
摘要
The reaction of 2,6-diisopropylaniline with m-phenylenedibenzimidoyl chloride 1,3-C6H4{N=C(Ph)Cl}2 in the presence of triethylamine in a toluene solution affords bis(amidine) 1,3-C6H4{NC(Ph)NH(2,6-iso-Pr2C6H3)}2 (H2L) in which two amidinate fragments are bound by the conformationally rigid m-phenylene linker. The metallation of bis(amidine) by n-butyllithium in the presence of tetramethylethylenediamine (TMEDA) occurs readily in a tetrahydrofuran solution at –70°С to form the corresponding lithium amidinate complex 1,3-C6H4{NC(Ph)N(2,6-iso-Pr2C6H3)}2Li2(TMEDA)2 (I). The X-ray structure analysis shows that complex I is monomeric (CIF file CCDC no. 1873201). Each amidinate fragment NCN is bound to one lithium atom via the κ2-N,N chelating mode.
288-294
Boron Cluster Anions [B10X10]2– (X = H, Cl) in Manganese(II) Complexation with 2,2'-Bipyridyl
摘要
The complexation of manganese(II) with 2,2'-bipyridyl in the presence of the [B10H10]2– and [B10Cl10]2– boron cluster anions has been studied in acetonitrile. The effect of the ratio of reagents on the composition and structure of final complexes has been shown. Mono- and binuclear manganese(II) complexes [(Mn(Bipy)3]2+ and [Mn2(Bipy)4Cl2]2+ have been synthesized with the boron cluster anions as counterions. The X-ray diffraction studies have been performed for complexes [Mn(Bipy)3][B10Cl (I)10] (I), [Mn(Bipy)3][B10Cl10]0.5[B10Cl9H]0.5 · CH3CN (III· CH3CN), and [Mn2(Bipy)4(µ-Cl)2][B10Cl10] · 2CH3CN (IV ⋅ 2CH3CN) (CIF files CCDC nos. 1868278 (I), 1868279 (III · CH3CN), 1868280 (IV · 2CH3CN)). Thermal properties of complex I have been studied.
295-300
Synthesis and Crystal Structures of the Reaction Products of the Magnesium Acenaphthenediimine Complex with Tosyl Azide
摘要
The reaction of [(Dpp-Bian)Mg(THF)3] (I) (Dpp-Bian is 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) with tosyl azide (TosN3) affords the binuclear amide complex [(Dpp-Bian)Mg(THF)(NTos)(THF)Mg(Dpp-Bian)] (II) in which the magnesium atoms are linked with the nitrogen atom by the bridging p-tolylsulfamide group. In the presence of pyridine, the reaction leads to the compound [(Dpp-Bian)Mg(Py)(NTos)(Py)Mg(Dpp-Bian)] (III) in which NTos has different coordination modes with the metal atoms. The diimine ligand is in the radical anion state in both compounds. New paramagnetic compounds II and III are characterized by IR spectroscopy, EPR spectroscopy, elemental analysis, and X-ray diffraction analysis (СFА files CCDC no. 1878433 (II · 1.5C5H12) and 1878432 (III · 2C7H8 · 0.5OC4H8)).
301-307