Palladium(II) complexes with R2edda-derived ligands

Four palladium(II) complexes with R₂edda ligands, dichlorido(O,O′-dialkylethylenediamine-N,N′-diacetate)palladium(II) monohydrates, [PdCl₂(R₂edda)]?H₂O, R = Me, Et, n-Pr, i-Bu, and the new ligand precursor i-Bu₂edda?2HCl?H₂O, O,O′-diisobutylethylenediamine-N,N′-diacetate dihydrochloride monohydrate, were synthesized and characterized by IR, ¹H and ¹³C NMR spectroscopy, and elemental analysis. DFT calculations were performed for the palladium(II) complexes and a high possibility for isomer formation due to stereogenic N ligand atoms was confirmed. Moreover, DFT simulations revealed energetic profile of isomer formation. Computational outcomes are in agreement with spectroscopic instrumental findings, both strongly indicating a non-stereoselective reaction between selected esters and K₂[PdCl₄], forming isomers.     

Mononuclear Formamidinate Complexes of Lithium and Sodium

Treatment of N,N′‐bis(aryl)formamidines (FXylH = N,N′‐bis(2,6‐dimethylphenyl)formamidine, FEtH = N,N′‐bis(2,6‐diethylphenyl)formamidine, FisoH = N,N′‐bis(2,6‐diisopropylphenyl)formamidine) with nBuLi in the presence of tmeda (= N,N,N′,N′‐tetramethylethylenediamine) led to deprotonation of the amidine affording [Li(FXyl)(tmeda)] ( 1 ), [Li(FEt)(tmeda)] ( 2 ) and [Li(Fiso)(tmeda)] ( 3 ) respectively. Similar treatment of FXylH and FisoH with [Na{N(SiMe₃)₂}] in THF and pmdeta (= N,N,N′,N″,N″‐pentamethyldiethylenetriamine) yielded [Na(FXyl)(pmdeta)] ( 4 ) and [Na(Fiso)(pmdeta)] ( 5 ). All complexes were characterised by spectroscopy (NMR and IR) and X‐ray crystallography. Due to the bulkiness of the formamidinate ligands and the multidentate nature of the supporting neutral amine ligands (tmeda and pmdeta), all compounds were mononuclear with η²‐chelating formamidinate ligands in the solid state.     

A highly porous metal-organic framework: structural transformations of a guest-free MOF depending on activation method and temperature

A doubly interpenetrating porous metal–organic framework ( SNU‐77 ) has been synthesized from the solvothermal reaction of the extended carboxylic acid tris(4′‐carboxybiphenyl)amine (H₃TCBPA) and Zn(NO₃)₂ ? 6H₂O in N,N‐dimethylacetamide (DMA). SNU‐77 undergoes single‐crystal‐to‐single‐crystal transformations during various activation processes, such as room‐temperature evacuation, supercritical CO₂ drying, and high temperature evacuation, to afford SNU‐77R , SNU‐77S , and SNU‐77H , respectively. These guest‐free MOFs exhibited different fine structures with different window shapes and different effective window sizes at room temperature. Variable‐temperature synchrotron single‐crystal X‐ray analyses reveal that the guest‐free structure is also affected by changes in temperature. Despite the different fine structures, SNU‐77R , SNU‐77S , and SNU‐77H show similar gas sorption properties due to the nonbreathing nature of the framework and an additional structural change upon cooling to cryogenic gas sorption temperature. SNU‐77H exhibits a large surface area (BET, 3670 m² g^?1), a large pore volume (1.52 cm³ g^?1), and exceptionally high uptake capacities for N₂, H₂, O₂, CO₂, and CH₄ gases.     

The first example of the stereoselective synthesis and crystal structure of a spirobicycloquinazolinone based on (–)‐fenchone and anthranilamide

The possibility of a single‐stage solvent‐free stereoselective synthesis of a spirocyclic compound from the natural bicyclic monoterpenoid (?)‐fenchone and anthranilamide has been shown for the first time. The molecular and crystal structure of (1R,2S,4S)‐1,3,3‐trimethyl‐1′H‐spiro[bicyclo[2.2.1]heptane‐2,2′‐quinazolin]‐4′(3′H)‐one, C₁₇H₂₂N₂O, was established by X‐ray diffraction though the chirality was assumed via the known reactant connectivity and ¹H and ¹³C NMR spectroscopy. It has shown that in the molecule, for steric reasons, there is an elongation of the Me₂C—C(N)N bond to 1.603 (5) Å. The formation of dimers via N—H…O=C hydrogen bonds with an interaction energy of 93.30 kJ mol^?1 and through cavities (33.7% of the unit‐cell volume) was established in the packing of the molecules. There are no π‐stacking interactions in the structure.     

Control of Interpenetration and Gas‐Sorption Properties of Metal–Organic Frameworks by a Simple Change in Ligand Design

In metal–organic framework (MOF) chemistry, interpenetration greatly affects the gas‐sorption properties. However, there is a lack of a systematic study on how to control the interpenetration and whether the interpenetration enhances gas uptake capacities or not. Herein, we report an example of interpenetration that is simply controlled by the presence of a carbon–carbon double or single bond in identical organic building blocks, and provide a comparison of gas‐sorption properties for these similar frameworks, which differ only in their degree of interpenetration. Noninterpenetrated ( SNU‐70 ) and doubly interpenetrated ( SNU‐71 ) cubic nets were prepared by a solvothermal reaction of [Zn(NO₃)₂] ? 6 H₂O in N,N‐diethylformamide (DEF) with 4‐(2‐carboxyvinyl)benzoic acid and 4‐(2‐carboxyethyl)benzoic acid, respectively. They have almost‐identical structures, but the noninterpenetrated framework has a much bigger pore size (ca. 9.0×9.0 Å) than the interpenetrated framework (ca. 2.5×2.5 Å). Activation of the MOFs by using supercritical CO₂ gave SNU‐70′ and SNU‐71′ . The simulation of the PXRD pattern of SNU‐71′ indicates the rearrangement of the interpenetrated networks on guest removal, which increases pore size. SNU‐70′ has a Brunauer–Emmett–Teller (BET) surface area of 5290 m² g^?1, which is the highest value reported to date for a MOF with a cubic‐net structure, whereas SNU‐71′ has a BET surface area of 1770 m² g^?1. In general, noninterpenetrated SNU‐70′ exhibits much higher gas‐adsorption capacities than interpenetrated SNU‐71′ at high pressures, regardless of the temperature. However, at P<1 atm, the gas‐adsorption capacities for N₂ at 77 K and CO₂ at 195 K are higher for noninterpenetrated SNU‐70′ than for interpenetrated SNU‐71′ , but the capacities for H₂ and CH₄ are the opposite; SNU‐71′ has higher uptake capacities than SNU‐70′ due to the higher isosteric heat of gas adsorption that results from the smaller pores. In particular, SNU‐70′ has exceptionally high H₂ and CO₂ uptake capacities. By using a post‐synthetic method, the C?C double bond in SNU‐70 was quantitatively brominated at room temperature, and the MOF still showed very high porosity (BET surface area of 2285 m² g^?1).     

Synthesis,characterization and crystal structures of the bidentate Schiff base N,N′‐bis(2‐nitrocinnamaldehyde)ethylenediamine and its complex with CuNCS and triphenylphosphane

Reaction of copper(I) thiocyanate and triphenylphosphane with the bidentate Schiff base N,N′‐bis(trans‐2‐nitrocinnamaldehyde)ethylenediamine {Nca₂en, (1); systematic name (1E,1′E,2E,2′E)‐N,N′‐(ethane‐1,2‐diyl)bis[3‐(2‐nitrophenyl)prop‐2‐en‐1‐imine]}, C₂₀H₁₈N₄O₄, in a 1:1:1 molar ratio in acetonitrile resulted in the formation of the complex {(1E,1′E,2E,2′E)‐N,N′‐(ethane‐1,2‐diyl)bis[3‐(2‐nitrophenyl)prop‐2‐en‐1‐imine]‐κ²N,N′}(thiocyanato‐κN)(triphenylphosphane‐κP)copper(I)], [Cu(NCS)(C₂₀H₁₈N₄O₄)(C₁₈H₁₅P)] or [Cu(NCS)(Nca₂en)(PPh₃)], (2). The Schiff base and copper(I) complex have been characterized by elemental analyses, IR, electronic and ¹H NMR spectroscopy, and X‐ray crystallography [from synchrotron data for (1)]. The molecule of (1) lies on a crystallographic inversion centre, with a trans conformation for the ethylenediamine unit, and displays significant twists from coplanarity of its nitro group, aromatic ring, conjugated chain and especially ethylenediamine segments. It acts as a bidentate ligand coordinating via the imine N atoms to the Cu^I atom in complex (2), in which the ethylenediamine unit necessarily adopts a somewhat flattened gauche conformation, resulting in a rather bowed shape overall for the ligand. The NCS⁻ ligand is coordinated through its N atom. The geometry around the Cu^I atom is distorted tetrahedral, with a small N—Cu—N bite angle of 81.56 (12)° and an enlarged opposite angle of 117.29 (9)° for SCN—Cu—P. Comparisons are made with the analogous Schiff base having no nitro substituents and with metal complexes of both ligands.     

Water Soluble Gold(I)‐diacetyl‐1,3,5‐triaza‐7‐phosphaadamantane‐arylazoimidazole Complexes: Synthesis and Spectroscopic Study

Reaction of [Au(DAPTA)(Cl)] with RaaiR’ in CH2Cl2 medium following ligand addition leads to [Au(DAPTA)(RaaiR’)](Cl) [DAPTA＝diacetyl-1,3,5-triaza-7-phosphaadamantane, RaaiR’＝p-R-C6H4-N＝N- C3H2-NN-1-R’, (1—3), abbreviated as N,N’-chelator, where N(imidazole) and N(azo) represent N and N’, respectively; R＝H (a), Me (b), Cl (c) and R’＝Me (1), CH2CH3 (2), CH2Ph (3)]. The 1H NMR spectral measurements in D2O suggest methylene, CH2, in RaaiEt gives a complex AB type multiplet while in RaaiCH2Ph it shows AB type quartets. 13C NMR spectrum in D2O suggest the molecular skeleton. The 1H-1H COSY spectrum in D2O as well as contour peaks in the 1H-13C HMQC spectrum in D2O assign the solution structure.     

NHC‐Containing Manganese(I) Electrocatalysts for the Two‐Electron Reduction of CO2

The synthesis and characterization of the first catalytic manganese N‐heterocyclic carbene complexes are reported: MnBr(N‐methyl‐N′‐2‐pyridylbenzimidazol‐2‐ylidine)(CO)₃ and MnBr(N‐methyl‐N′‐2‐pyridylimidazol‐2‐ylidine)(CO)₃. Both new species mediate the reduction of CO₂ to CO following two‐electron reduction of the Mn^I center, as observed with preparative scale electrolysis and verified with ¹³CO₂. The two‐electron reduction of these species occurs at a single potential, rather than in two sequential steps separated by hundreds of millivolts, as is the case for previously reported MnBr(2,2′‐bipyridine)(CO)₃. Catalytic current enhancement is observed at voltages similar to MnBr(2,2′‐bipyridine)(CO)₃.     

Post‐Synthetic Reversible Incorporation of Organic Linkers into Porous Metal–Organic Frameworks through Single‐Crystal‐to‐Single‐Crystal Transformations and Modification of Gas‐Sorption Properties

The porous metal–organic framework (MOF) {[Zn₂(TCPBDA)(H₂O)₂]?30 DMF?6 H₂O}_n ( SNU‐30 ; DMF=N,N‐dimethylformamide) has been prepared by the solvothermal reaction of N,N,N′,N′‐tetrakis(4‐carboxyphenyl)biphenyl‐4,4′‐diamine (H₄TCPBDA) and Zn(NO₃)₂?6 H₂O in DMF/tBuOH. The post‐synthetic modification of SNU‐30 by the insertion of 3,6‐di(4‐pyridyl)‐1,2,4,5‐tetrazine (bpta) affords single‐crystalline {[Zn₂(TCPBDA)(bpta)]?23 DMF?4 H₂O}_n ( SNU‐31 SC ), in which channels are divided by the bpta linkers. Interestingly, unlike its pristine form, the bridging bpta ligand in the MOF is bent due to steric constraints. SNU‐31 can be also prepared through a one‐pot solvothermal synthesis from Zn^II, TCPBDA^4?, and bpta. The bpta linker can be liberated from this MOF by immersion in N,N‐diethylformamide (DEF) to afford the single‐crystalline SNU‐30 SC , which is structurally similar to SNU‐30 . This phenomenon of reversible insertion and removal of the bridging ligand while preserving the single crystallinity is unprecedented in MOFs. Desolvated solid SNU‐30′ adsorbs N₂, O₂, H₂, CO₂, and CH₄ gases, whereas desolvated SNU‐31′ exhibits selective adsorption of CO₂ over N₂, O₂, H₂, and CH₄, thus demonstrating that the gas adsorption properties of MOF can be modified by post‐synthetic insertion/removal of a bridging ligand.     

Conversion of substituted 5‐aryloxypyrazolecarbaldehydes into reduced 3,4′‐bipyrazoles: synthesis and characterization,and the structures of four precursors and two products,and their supramolecular assembly in zero,one and two dimensions

The reaction of 5‐chloro‐3‐methyl‐1‐phenyl‐1H‐pyrazole‐4‐carbaldehyde with phenols under basic conditions yields the corresponding 5‐aryloxy derivatives; the subsequent reaction of these carbaldehydes with substituted acetophenones yields the corresponding chalcones, which in turn undergo cyclocondensation reactions with hydrazine in the presence of acetic acid to form N‐acetylated reduced bipyrazoles. Structures are reported for three 5‐aryloxycarbaldehydes and the 5‐piperidino analogue, and for two reduced bipyrazole products. 5‐(2‐Chlorophenoxy)‐3‐methyl‐1‐phenyl‐1H‐pyrazole‐4‐carbaldehyde, C₁₇H₁₃ClN₂O₂, (II), which crystallizes with Z′ = 2 in the space group P, exhibits orientational disorder of the carbaldehyde group in each of the two independent molecules. Each of 3‐methyl‐5‐(4‐nitrophenoxy)‐1‐phenyl‐1H‐pyrazole‐4‐carbaldehyde, C₁₇H₁₃N₃O₄, (IV), 3‐methyl‐5‐(naphthalen‐2‐yloxy)‐1‐phenyl‐1H‐pyrazole‐4‐carbaldehyde, C₂₁H₁₆N₂O₂, (V), and 3‐methyl‐1‐phenyl‐5‐(piperidin‐1‐yl)‐1H‐pyrazole‐4‐carbaldehyde, C₁₆H₁₉N₃O, (VI), (3RS)‐2‐acetyl‐5‐(4‐azidophenyl)‐5′‐(2‐chlorophenoxy)‐3′‐methyl‐1′‐phenyl‐3,4‐dihydro‐1′H,2H‐[3,4′‐bipyrazole] C₂₇H₂₂ClN₇O₂, (IX) and (3RS)‐2‐acetyl‐5‐(4‐azidophenyl)‐3′‐methyl‐5′‐(naphthalen‐2‐yloxy)‐1′‐phenyl‐3,4‐dihydro‐1′H,2H‐[3,4′‐bipyrazole] C₃₁H₂₅N₇O₂, (X), has Z′ = 1, and each is fully ordered. The new compounds have all been fully characterized by analysis, namely IR spectroscopy, ¹H and ¹³C NMR spectroscopy, and mass spectrometry. In each of (II), (V) and (IX), the molecules are linked into ribbons, generated respectively by combinations of C—H…N, C—H…π and C—Cl…π interactions in (II), C—H…O and C—H…π hydrogen bonds in (V), and C—H…N and C—H…O hydrogen bonds in (IX). The molecules of compounds (IV) and (IX) are both linked into sheets, by multiple C—H…O and C—H…π hydrogen bonds in (IV), and by two C—H…π hydrogen bonds in (IX). A single C—H…N hydrogen bond links the molecules of (X) into centrosymmetric dimers. Comparisons are made with the structures of some related compounds.     

Lanthanide Complexes of Polyacid Ligands derived from 2, 6-bis(pyrazol-1-yl)pyridine,pyrazine, and 6, 6′-bis(pyrazol-1-yl)-2, 2′-bipyridine: Synthesis and luminescence properties

The synthesis of three novel pyrazole-containing complexing acids, N,N,N′,N′-{2, 6-bis[3-(aminomethyl)pyrazol-1-yl]-4-methoxypyridine}tetrakis(acetic acid)( 1 ), N,N,N′,N′-{2, 6-bis[3-(aminomethyl)pyrazol-1-yl]pyrazine}-tetrakis(acetic acid) ( 2 ), and N,N,N′,N′-{6, 6′-bis[3-(aminomethyl)pyrazol-1-yl]-2, 2′-bipyridine}tetrakis(acetic acid) ( 3 ) is described. Ligands 1–3 formed stable complexes with Eu^III, Tb^III, Sm^III, and Dy^III in H₂O whose relative luminescence yields, triplet-state energies, and emission decay lifetimes were measured. The number of H₂O molecules in the first coordination sphere of the lanthanide ion were also determined. Comparison of data from the Eu^III and Tb^III complexes of 1–3 and those of the parent trisheterocycle N,N,N′,N′-{2, 6-bis[3-(aminomethyl)pyrazol-l-yl]pyridine}tetrakis(acetic acid) showed that the modification of the pyridine ring for pyrazine or 2, 2′-bipyridine strongly modify the luminescence properties of the complexes. MeO Substitution at C(4) of 1 maintain the excellent properties described for the parent compound and give an additional functional group that will serve for attaching the label to biomolecules in bioaffinity applications.     

Organic Diodes Based on Redox-Polymer Bilayer-Film-Modified Electrodes

The synthesis of four electropolymerizable 2,2′-bipyridinium salts with tuned reduction potential (E₁^°) is described (N,N′-ethylene-4-methyl-4′-vinyl-2,2′-bipyridinium dibromide ( 4 ; E₁^° ?–0.48 V), 4-methyl-N, N′-(trimethylene)-4′-vinyl-2,2′-bipyridinium dibromide ( 5 ; E₁^°? ?0.66 V), N,N′-ethylene-4-methyl-4′-[2-(1H-pyrrol-1-yl)ethyl]-2, 2′-bipyridinium bis(hexafluorophosphate) ( 6b ; E₁^°? ?0.46 V), and 4-methyl-4′-[2-(1H-pyrrol-1-yl)ethyl]-N, N′-(trimethylene)-2,2′-bipyridinium bis(hexafluorophosphate) ( 7b ; E₁^°? ?0.66 V)). E₁^°-Tuning is based on the torsional angle C(3)–C(2)–C(2′)–C(3′), imposed by the N,N′-ethylene and N,N′-(trimethylene) bridge. The vinylic compounds 4 and 5 undergo cathodic, the pyrrole derivatives 6b and 7b anodic electropolymerization on glassy carbon electrodes from MeCN solutions, yielding thin, surface-confined films with surface concentrations of redox-active material in the range 5 · 10^?9 < Γ < 2.10^?8 mol/cm², depending on experimental conditions. The modified electrodes exhibit reversible ‘diquat’ electrochemistry in pure solvent/electrolyte. Copolymerization of 6b or 7b with pyrrole yields most stable electrodes. Bi ayer-film-modified electrodes were prepared by sequential electropolymerization of the monomers. The assembly electrode/poly- 6b /poly- 7b behaves as a switch, it transforms – as a Schmitt trigger – an analog input signal (the electrode potential) into a digital output signal (redox state of the outer polymer film). Forward-(electrode/poly- 7b /poly- 6b ) and reverse-biased assemblies (electrode/poly- 6b /poly- 7b ) were coupled to the electrochemical reduction of redox-active solution species, e.g. N- (cyanomethyl)-N′-methyl-4,4′-bipyridinium bis(hexafluorophosphate) ( 8 ). Zener-diode-like behavior was observed. Aspects of redox-polymer multilayer-film assemblies, sandwiched between two electronic conductors, are discussed in terms of molecular electronic devices.     

Synthesis and conformational properties of 2′-deoxy-2′-methylthio-pyrimidine and -purine nucleosides: Potential antisense applications

A convenient and shorter synthesis of 2′-deoxy-2′-methylthiouridine analogs 5 , ?5-methyluridine 6 , -cyti-dine 15 , ?5-methylcytidine 16 , -adenosine 27 and -guanosine 34 was accomplished. Successful conversion of ribonucleosides (5-methyl U, U, A, G) into the corresponding 2′-substituted nucleosides involves nucleophilic displacement (S_N2) of an appropriate leaving group at the 2′-position by methanethiol, a soft nucleophile. Reaction between 2,2′-anhydrouridine and methanethiol in the presence of N¹,N¹,N³,N³-tetramethylguani-dine in N,N-dimethylformamide gave 5 , in 75% yield. Preparation of 6 by a similar route was described. Acylated 5 and 6 were transformed into their triazole derivatives, which on ammonolysis furnished 15 and 16 , respectively in good yield. Similarly, tetraisopropyldisiloxanyl (TIPS) protected 2′-O-aratriflates- of-adenosine and -guanosine reacted with methanethiol in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene at - 25°, followed by deblocking of the TIPS protecting group furnished 27 and 34 , respectively. The confor-mational flexibility (N/S equilibrium) of the sugar moiety in nucleosides 5 , 15 , 27 and 34 was studied utilizing nmr spectroscopy, suggesting that the 2′-methylthio group influenced the sugar conformation to adopt a rigid S-pucker in all cases. The extra stiffness of the sugar moiety in these analogs is believed to be due to the electronegativity of the substituent and the steric bulk. The usefulness of these nucleosides to prepare uniformly modified 2′-deoxy-2′-methylthio oligonucleotides for antisense therapeutics is proposed.     

Dinuclear Complexes of Copper(I) with Crown Ether‐containing N‐Thiophosphorylated Bis‐thioureas and 2,2′‐Bipyridine or 1,10‐Phenanthroline: Synthesis,Characterization, and Picrate Extraction Properties

Reaction of O,O′‐diisopropylthiophosphoric acid isothiocyanate (iPrO)₂P(S)NCS with 1,10‐diaza‐18‐crown‐6, 1,7‐diaza‐18‐crown‐6, or 1,7‐diaza‐15‐crown‐5 leads to the N‐thiophosphorylated bis‐thioureas N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 ( H₂L^I ), N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐18‐crown‐6 ( H₂L^II ) and N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐15‐crown‐5 ( H₂L^III ). Reaction of the potassium salts of H₂L^I–III with a mixture of CuI and 2,2′‐bipyridine ( bpy ) or 1,10‐phenanthroline ( phen ) in aqueous EtOH/CH₂Cl₂ leads to the dinuclear complexes [Cu₂(bpy)₂L^I–III] and [Cu₂(phen)₂L^I–III] . The structures of these compounds were investigated by ¹H, ³¹P{¹H} NMR spectroscopy, and elemental analysis. The crystal structures of H₂L^I and [Cu₂(phen)₂L^I] were determined by single‐crystal X‐ray diffraction. Extraction capacities of the obtained compounds in comparison to the related compounds 1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(=CMe₂)CH₂P(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(S)NHP(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 towards the picrate salts LiPic, NaPic, KPic. and NH₄Pic were also studied.     

Reactivity of ortho‐Substituted Aryl–Palladium Complexes towards Carbodiimides,Isothiocyanates, Nitriles,and Cyanamides

Complexes [Pd(C₆H₃XH‐2‐R′‐5)Y(N^N)] (X=O, NH; Y=Br, I; R′=H, NO₂; N^N=N,N,N′,N′‐tetramethylethylenediamine (tmeda), 2,2′‐bipyridine (bpy), 4,4′‐di‐tert‐butyl‐2,2′‐bipyridine (dtbbpy)) react with RN?C?E (E=NR, S) or RC≡N (R=alkyl, aryl, NR′′₂) and TlOTf (OTf=CF₃SO₃) to give, respectively, 1) products of the insertion of the C?E group into the C? Pd bond, protonation of the N atom, and coordination of X to Pd, [Pd{κ²‐X,E‐(XC₆H₃{EC(NHR)}‐2‐R′‐4)}(N^N)]OTf or [Pd(κ²‐X,N‐{ZC₆H₃(NH?CR)‐2‐R′‐4})(N^N)]OTf, or products of the coordination of carbodiimides and OH addition, [Pd{κ²‐C,N‐(C₆H₄{OC(NR)}NHR‐2)}(bpy)]OTf; or 2) products of the insertion of the C≡N group to Pd and N‐protonation, [Pd(κ²‐X,N‐{XC₆H₃(NH?CR)‐2‐R′‐4})(N^N)]OTf.     

Ligand Substitution Reactions on Aquapentachloro‐ and Hexachloroplatinic Acid — Synthesis and Characterization of Tetrachloroplatinum(IV) Complexes with Heterocyclic N,N Donors

Reactions of aquapentachloroplatinic acid, (H₃O)[PtCl₅(H₂O)]·2(18C6)·6H₂O ( 1 ) (18C6 = 18‐crown‐6), and H₂[PtCl₆]·6H₂O ( 2 ) with heterocyclic N, N donors (2, 2′‐bipyridine, bpy; 4, 4′‐di‐tert‐butyl‐2, 2′‐bipyridine, tBu₂bpy; 1, 10‐phenanthroline, phen; 4, 7‐diphenyl‐1, 10‐phenanthroline, Ph₂phen; 2, 2′‐bipyrimidine, bpym) afforded with ligand substitution platinum(IV) complexes [PtCl₄(N∩N)] (N∩N = bpy, 3a ; tBu₂bpy, 3b ; Ph₂phen, 5 ; bpym, 7 ) and/or with protonation of N, N donor yielding (R₂phenH)₂[PtCl₆] (R = H, 4a ; Ph, 4b ) and (bpymH)⁺ ( 8 ). With UV irradiation Ph₂phen and bpym reacted with reduction yielding platinum(II) complexes [PtCl₂(N∩N)] (N∩N = Ph₂phen, 6 ; bpym, 9 ). Identities of all complexes were established by microanalysis as well as by NMR (¹H, ¹³C, ¹⁹⁵Pt) and IR spectroscopic investigations. Molecular structures of [PtCl₄(bpym)]·MeOH ( 7 ) and [PtCl₂(Ph₂phen)] ( 6 ) were determined by X‐ray diffraction analyses. Differences in reactivity of bpy/bpym and phen ligands are discussed in terms of calculated structures of complexes [PtCl₅(N∩N)]^— with monodentately bound N, N ligands (N∩N = bpy, 10a ; phen, 10b ; bpym, 10c ).     

Front Cover: Small-Molecule Activation by Heteroleptic Metallasilylenes (Eur. J. Inorg. Chem. 2/2023)

We report on reactions of heteroleptic metallasilylenes L¹(Cl)MSiL² (M=Al 1 , Ga 2 , L¹=HC[C(Me)NDipp]₂, Dipp=2,6-ⁱPr₂C₆H₃; L²=PhC(N^tBu)₂) with CO₂, N₂O, and Me₃SiN₃, yielding the corresponding carbonate complexes L¹(Cl)MOSi(CO₃-κ²O,O−)L² (M=Al 3 , Ga 4 ), silanoic esters L¹(Cl)MOSi(O)L² (M=Al 5 , Ga 6 ), and silaimine L¹(Cl)GaSi(NSiMe₃)L² ( 8 ), whereas {L²Si[N(SiMe₃)Al(Cl)C(Me)NDipp][CHC(Me)N(Dipp)]} 7 was formed by C−C bond cleavage of the L¹ ligand. Compounds 3 – 8 were characterized by NMR (¹H, ¹³C) and IR spectroscopy, elemental analysis and single crystal X-ray diffraction.     

Synthesis and characterization of a novel organic–inorganic hybrid salt and its application as a highly effectual Brønsted–Lewis acidic catalyst for the production of N,N′‐alkylidene bisamides

In this research, a novel organic–inorganic hybrid salt, namely, N¹,N¹,N²,N²‐tetramethyl‐N¹,N²‐bis(sulfo)ethane‐1,2‐diaminium tetrachloroferrate ([TMBSED][FeCl₄]₂) was prepared and characterized by Fourier‐transform infrared spectroscopy (FT‐IR), energy‐dispersive X‐ray spectroscopy (EDX), elemental mapping, field emission scanning electron microscopy (FE‐SEM), X‐ray diffraction (XRD), thermal gravimetric (TG), differential thermal gravimetric (DTG), and vibrating‐sample magnetometry (VSM) analyses. Catalytic activity of the hybrid salt was tested for the synthesis of N,N′‐alkylidene bisamides through the reaction of benzamide (2 eq.) and aromatic aldehydes (1 eq.) under solvent‐free conditions in which the products were obtained in high yields and short reaction times. The catalyst was superior to many of the reported catalysts in terms of two or more of these factors: the reaction medium and temperature, yield, time, and turnover frequency (TOF). [TMBSED][FeCl₄]₂ is a Brønsted–Lewis acidic catalyst; there are two SO₃H groups (as Brønsted acidic sites) and two tetrachloroferrate anions (as Lewis acidic sites) in its structure. Highly effectiveness of the catalyst for the synthesis of N,N′‐alkylidene bisamides can be attributed to synergy of the Brønsted and Lewis acids and also possessing two sites of each acid.     

Studies on reactions of some ruthenium sulfoxide bipyridyl complexes with 1,4-bis(salicylidene)phenylenediamine ligand used as spacer

A dinucleating spacer 1,4-bis(salicylidene)phenylenediamine (SALPHEN) derived from 1,4-phenylenediamine and salicylaldehyde has been synthesized and characterized. The ruthenium(II) sulfoxide derivative of 2,2′-bipyridine or 1,10-phenanthroline on reaction with this ligand resulted in the formation of eight dinuclear complexes, which were characterized by elemental analyses, conductivity measurements, magnetic susceptibility, FT-IR, fast atom bombardment-mass spectra, electronic spectroscopy, ¹H-NMR, ¹³C{¹H}-NMR, and ²D-NMR spectra (HETCOR). The prepared complexes have two different formulations, [{trans-RuCl₂(so)(N–N′)}₂(μ-SALPHEN)] and [{cis-RuCl₂(so)(N–N′)}₂(μ-SALPHEN)], where so?=?dimethyl sulfoxide (DMSO)/tetramethylene sulfoxide (TMSO), N–N′?=?2,2′-bipyridine/1,10-phenanthroline, and SALPHEN?=?1,4-bis(salicylidene)phenylenediamine. Two moles of ruthenium sulfoxide bipyridine precursor were coordinated to the bidentate SALPHEN through nitrogen. All the complexes possess antibacterial activity against Escherichia coli in comparison to Chloramphenicol.     

Engineered Bifunctional Luminescent Pillared-Layer Frameworks for Adsorption of CO2 and Sensitive Detection of Nitrobenzene in Aqueous Media

Through a dual-ligand synthetic approach, five isoreticular primitive cubic (pcu)-type pillared-layer metal–organic frameworks (MOFs), [Zn₂(dicarboxylate)₂(NI-bpy-44)] ⋅ x DMF ⋅ y H₂O, in which dicarboxylate=1,4-bdc ( 1 ), Br-1,4-bdc ( 2 ), NH₂-1,4-bdc ( 3 ), 2,6-ndc ( 4 ), and bpdc ( 5 ), have been engineered. MOFs 1 – 5 feature twofold degrees of interpenetration and have open pores of 27.0, 33.6, 36.8, 52.5, and 62.1 %, respectively. Nitrogen adsorption isotherms of activated MOFs 1′ – 5′ at 77 K all displayed type I adsorption behavior, suggesting their microporous nature. Although 1′ and 3′ – 5′ exhibited type I adsorption isotherms of CO₂ at 195 K, MOF 2′ showed a two-step gate-opening sorption isotherm of CO₂. Furthermore, MOF 3′ also had a significant influence of amine functions on CO₂ uptake at high temperature due to the CO₂–framework interactions. MOFs 1 – 5 revealed solvent-dependent fluorescence properties; their strong blue-light emissions in aqueous suspensions were efficiently quenched by trace amounts of nitrobenzene (NB), with limits of detection of 4.54, 5.73, 1.88, 2.30, and 2.26 μm , respectively, and Stern–Volmer quenching constants (K_sv) of 2.93×10³, 1.79×10³, 3.78×10³, 4.04×10³, and 3.21×10³ m ⁻¹, respectively. Of particular note, the NB-included framework, NB@ 3 , provided direct evidence of the binding sites, which showed strong host–guest π–π and hydrogen-bonding interactions beneficial for donor–acceptor electron transfer and resulting in fluorescence quenching.