Ferrocenophanes with Interannular Nitrogen–Gallium Bridges. 1,3,2‐Diazagalla‐[3]Ferrocenophanes and an 1‐Aza‐3‐Azonia‐2‐Gallata‐[3]Ferrocenophane. Synthesis and Structure

1,1′‐Bis(trimethylsilylamino)ferrocene reacts with trimethyl‐ and triethylgallium to give the μ‐[ferrocene‐1,1′‐diyl‐bis(trimethylsilylamido)]tetraalkyldigallanes. These were converted into the 1,3‐bis(trimethylsilyl)‐2‐alkyl‐2‐pyridine‐1,3,2‐diazagalla‐[3]ferrocenophanes, of which the ethyl derivative was characterized by X‐ray structural analysis. Treatment of gallium trichloride with N,N′‐dilithio‐1,1′‐bis(trimethylsilylamino)ferrocene affords μ‐[ferrocene‐1,1′‐diyl‐bis(trimethylsilylamido)]tetrachlorodigallane along with bis(trimethylsilyl)‐2,2‐dichloro‐1‐aza‐3‐azonia‐2‐gallata‐[3]ferrocenophane as a side product, and both were structurally characterized by X‐ray analysis. The solution‐state structures of the new gallium compounds and aspects of their molecular dynamics in solution were studied by NMR spectroscopy (¹H, ¹³C, ²⁹Si NMR).     

Biological studies of newly synthesized ferrocenyl complexes containing triazinone moiety

A new ferrocenyl ligand, 1,1′‐bis[1‐methyl‐5‐phenyl‐4H‐(1,3,4)‐thiadiazolo(2,3‐c)(1,2,4)triazin‐4‐one]ferrocene was prepared from the reaction of 1,1′‐diacetylferrocene with 4‐amino‐2,3‐dihydro‐6‐phenyl‐3‐thioxo[1,2,4]triazin‐5(4H)one. The ligand, L, forms 1:1 complexes with Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) in good yield. Characterization of the ligand and its complexes was carried out using IR, ¹H NMR, magnetic susceptibility as well as elemental analysis. Biological activity of the ligand and its complexes were carried out against Aspergillus niger, Cladosporium herbirum and Fusarium moniliformae using filter paper discs; and against bacterial strains of Escherichia coli, Staphylococcus aureus using viable cell counting technique. The results indicated that the ligand is biologically active whereas the complexes are more active than the ligand. Copyright © 2006 John Wiley & Sons, Ltd.     

Synthesis,characterization and biocidal studies of new ferrocenyl thiadiazolo‐triazinone complexes

One‐pot synthesis of ferrocenyl ligand, 1,1′‐bis[1,5‐methyl‐4H‐(1,3,4)‐thiadiazolo(2,3‐c)(1,2,4)triazin‐4‐one]ferrocene was prepared from the reaction of 1,1′‐diacetylferrocene with 4‐amino‐2,3‐dihydro‐6‐methyl‐3‐thioxo[1,2,4]triazin‐5(4H)one. The ligand, L, forms 1:1 complexes with Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) in good yield. Characterization of the ligand and its complexes was carried out using IR, ¹H NMR, magnetic susceptibility as well as elemental analysis. Biocidal activity of the ligand and its complexes were determined against the standard fungal strains of Aspergillus niger, Cladosporium herbarum and Fusarium moniliforme using the paper disc diffusion method; and against bacterial strains of Escherichia coli and Staphylococcus aureus using viable cell counting technique. The results indicated that the complexes are biologically more active than the free ligand. The biocidal activity depends on the metal ion, concentration as well as the tested fungi and bacteria. Copyright © 2006 John Wiley & Sons, Ltd.     

Synthesis,characterization and biological studies of ferrocenyl complexes containing thiophene moiety

A new ferrocenyl ligand was prepared from the condensation of 1,1′‐diacetylferrocene dihydrazone with 2‐thiophenealdehyde. The ligand, 1,1′‐bis[(2‐thienylmethylidene)hydrazono‐1‐ethyl]ferrocene, forms 1:1 complexes with cobalt(II), nickel(II), copper(II) and zinc(II) in good yield. Characterization of the ligand and complexes was carried out using IR, ¹H NMR, electronic absorption and elemental analysis. Biological activity of the ligand and its complexes was assessed against Bacillus subtilis (+ve), Staphylococcus aureus (+ve), Candida albicans (yeast), Esherichia coli (?ve), Salmonella typhi (?ve), Aspergillus niger (fungi), and Fusarium solani (fungi). The biological results indicated that the complexes prepared are more active than the ligand. Copyright © 2005 John Wiley & Sons, Ltd.     

Spiro Compounds of Tin,Selenium and Tellurium Containing 1,3,2‐Diazaelement‐[3]ferrocenophane Units

The reactions of 1,1′‐bis[Li(trimethylsilyl)amino]ferrocene ( 2a ) with selenium‐ or tellurium tetrahalides gave the 1,1′,3,3′‐tetrakis(trimethylsilyl)‐1,1′,3,3′‐tetraaza‐2‐selene‐ and 2‐tellura‐2,2′‐spirobi[3]ferrocenophanes 5 and 6 , respectively. The analogous reaction with tin dichloride afforded the corresponding 2‐stanna‐2,2′‐spirobi[3]ferrocenophane ( 9 ) rather than the expected stannylene 8 . The reaction of 2,2‐dichloro‐1,3‐bis(trimethylsilyl)‐1,3,2‐diazastanna‐[3]ferrocenophane ( 10 ) with the dilithio reagent 2b also gave the spirotin compound 9 , of which the molecular structure was determined by X‐ray analysis. The formation of the products and their solution‐state structures was deduced from multinuclear magnetic resonance spectroscopic studies (¹H, ¹³C, ¹⁵N, ²⁹Si, ⁷⁷Se, ¹²⁵Te, ¹¹⁹Sn NMR spectroscopy).     

Iron(II)‐ and Cobalt(II) Complexes with Tridentate Bis(imino)pyridine Nitrogen Ligands Bearing Chiral Bulky Aliphatic and Aromatic Substituents: Crystal Structure of [CoCl2{2, 6‐bis[R‐(+)‐(bornylimino)methyl]pyridine}]

Iron(II) and cobalt(II) complexes ( 7 ‐ 15 ) based on new aldimine 2, 6‐bis[(imino)methyl]pyridine ( 1 , 2 , 4 , 6 ) and ketimine (2, 6‐bis[(imino)ethyl]pyridine ( 3 , 5 ) ligands with bulky chiral aliphatic or aromatic terminal groups have been prepared and characterized by ¹H NMR, ¹³C NMR, IR‐, mass spectroscopy (EI), and elemental analysis. The complex [CoCl₂(BBoMP)]·¹/₂ CHCl₃ ( 13 ) (BBoMP: 2, 6‐bis{(R‐(+)‐(bornylimino)‐methyl}pyridine) crystallizes in monoclinic space group P2₁ with cell dimensions: a = 7.6603(11) Å, b = 28.3153(14) Å, c = 13.537(2) Å, V = 2908.1(6) ų, Z = 4. The coordination sphere around Co is distorted trigonal bipyramidal.     

A one‐dimensional zinc(II) coordination polymer incorporating [1,1′‐biphenyl]‐4,4′‐dicarboxylate and N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide ligands

In the title compound, catena‐poly[[[N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide]chloridozinc(II)]‐μ‐[1,1′‐biphenyl]‐4,4′‐dicarboxylato‐[[N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide]chloridozinc(II)]‐μ‐[N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide]], [Zn₂(C₁₄H₈O₄)Cl₂(C₂₆H₂₂N₄O₂)₃]_n, the Zn^II centre is four‐coordinate and approximately tetrahedral, bonding to one carboxylate O atom from a bidentate bridging dianionic [1,1′‐biphenyl]‐4,4′‐dicarboxylate ligand, to two pyridine N atoms from two N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide ligands and to one chloride ligand. The pyridyl ligands exhibit bidentate bridging and monodentate terminal coordination modes. The bidentate bridging pyridyl ligand and the bridging [1,1′‐biphenyl]‐4,4′‐dicarboxylate ligand both lie on special positions, with inversion centres at the mid‐points of their central C—C bonds. These bridging groups link the Zn^II centres into a one‐dimensional tape structure that propagates along the crystallographic b direction. The tapes are interlinked into a two‐dimensional layer in the ab plane through N—H...O hydrogen bonds between the monodentate ligands. In addition, the thermal stability and solid‐state photoluminescence properties of the title compound are reported.     

Effect of Chelate Ring Size in Iron(II) Isothiocyanato Complexes with Tetradentate Tripyridyl‐alkylamine Ligands on Spin Crossover Properties

Iron(II) complexes of the type [Fe(L)(NCS)₂] with tetradentate ligands L are well known to show spin crossover properties. However, this behavior is quite sensitive in regard to small changes of the ligand system. Starting from the thoroughly investigated complex [Fe(tmpa)(NCS)₂] [tmpa = tris(2‐pyridylmethyl)amine, also abbreviated as tpa in the literature] we modified the ligand by increasing systematically the chelate ring sizes from 5 to 6 thus obtaining complexes [Fe(pmea)(NCS)₂], [Fe(pmap)(NCS)₂], and [Fe(tepa)(NCS)₂] [pmea = N,N‐bis[(2‐pyridyl)methyl]‐2‐(2‐pyridyl)ethylamine, pmap = N,N‐bis[2‐(2‐pyridyl)ethyl]‐(2‐pyridyl)methylamine, and tepa = tris[2‐(2‐pyridyl)ethyl]amine]. All complexes were structurally characterized and spin crossover properties were investigated using Mößbauer spectroscopy, magnetic measurements, and IR/Raman analyses. The results demonstrated that only the iron complexes with tmpa and pmea showed spin crossover properties, whereas the complexes with the ligands pmap and tepa only formed high spin complexes. Furthermore, DFT calculations supported these findings demonstrating again the strong influence of ligand environment. Herein the effect of increasing the chelate ring sizes in iron(II) isothiocyanato complexes with tetradentate tripyridyl‐alkylamine ligands is clearly demonstrated.     

A New Ferrocene‐Containing Polyamide Prepared from an Improved Synthesis of 1,1′‐Ferrocene Dicarbonyl Chloride and Ferrocene‐Based Diamine

1,1′‐Ferrocene dicarbonyl chloride was prepared by an improved and efficient conversion method from 1,1′‐ferrocene dicarboxylic acid and reacted by esterification with p‐nitrophenol, followed by reduction, to form a ferrocene‐based diamine, 1,1′‐ferrocene bis (p‐amino phenylate). The diamine was characterized by elemental analysis, ¹H NMR, and Fourier transform infrared (FTIR) spectroscopy and subsequently condensed with 1,1′‐ferrocene dicarbonyl chloride to form a novel main chain ferrocene‐containing polyamide, poly{imino ferrocene bis (p‐amino phenylate) ferrocenyl}. Its polymeric nature was confirmed by its physical properties, elemental analysis, FTIR spectroscopy, differential scanning calorimetry, and thermogravimetric studies.     

Three new vic‐dioxime ligands: Synthesis,characterization, spectroscopy,and redox properties of their mononuclear nickel(II) complexes

Nickel(II) complexes with three new vic‐dioxime reagents, N‐(ethyl‐4‐amino‐1‐piperidine carboxylate)phenylglyoxime (L₁H₂), N‐(ethyl‐4‐amino‐1‐piperidine carboxylate)glyoxime (L₂H₂) and N,N′‐bis(ethyl‐4‐amino‐1‐piperidine carboxylate)glyoxime (L₃H₂), have been prepared. Mononuclear nickel(II) complexes with a metal/ligand ratio of 1:2 were prepared using Ni(II) salt. All these nickel(II) complexes are nonelectrolytes as shown by their molar conductivities (Λ_M) in DMF solution at 10⁻³ M concentration. The ligands are soluble in common solvents such as DMSO, DMF, CHCl₃, and C₂H₅OH. The ligands and their Ni(II) complexes were characterized by elemental analyses, FT‐IR, UV‐visible, ¹H NMR, ¹³C NMR, magnetic susceptibility measurements, cyclic voltammetry, and molar conductivities (Λ_M). The cyclic voltammetric measurements show that [Ni(L₁H)₂] and [Ni(L₂H)₂] complexes exhibit almost similar electrochemical behavior, with two reduction and two oxidation processes based on either metals or oxime moities, while [Ni(L₃H)₂⋅2H₂O] complex displays irreversible, with one reduction and one oxidation processes based on oxime moity. This main difference could be attributed to the highly polarized [Ni(L₃H)₂⋅2H₂O] complex that has four carboxylate groups attached to piperidine on the oxime moieties. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:657–663, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20357     

Synthesis,spectroscopic and thermal properties of Pt(II) complexes of some polydentate ligands

The new tetradentate symmetrical (2R,2′S)-1,1′-piperazine-1,4-diyldipropane-2-thiol) (L¹), (2S)-1-[bis(2-aminoethyl)amino]propan-2-ol) (L²), and 2-{(E)-[((1R,2S)-2-{[(1Z)-(2-hydroxy phenyl)methylene]amino}cyclohexyl)imino]methyl}phenol (L³) ligands were synthesized and characterized on the basis of FT-IR, ¹H, ¹³C NMR, EI mass, and elemental analysis. Three commercially available ligands, (2,2′-[ethane-1,2-diylbis(thio)]diethanol (L⁴), 2,2′-dithiodiethanenamine (L⁵), and (2,2′-[ethane-1,2-diyldi(imino)] diethanol (L⁶), were also studied. Pt(II) complexes were characterized by FTIR, elemental analysis and thermal methods. Thermal behaviors of these complexes were investigated in the range 10–1000 °C. Magnetic properties were also studied, and the all complexes were found to be diamagnetic. The structures consist of the monomeric units in which the Pt(II) atoms exhibit square planar geometry. N,N′-bis(salicylidene)-1,2-cyclohexane has been synthesized and characterized by X-ray single crystal diffraction measurement. The ligand crystallizes in monoclinic crystal system and space group, Cc.     

Sterically‐Directed Consecutive and Size‐Selective Self‐Assembly of Palladium Diphosphane Complexes with an Ar‐BIAN Ligand: Unexpected Formation of Pentameric and Hexameric Aggregates

The coordination properties of N,N′‐bis[4‐(4‐pyridyl)phenyl]acenaphthenequinonediimine (L¹) and N,N′‐bis[4‐(2‐pyridyl)phenyl]acenaphthenequinonediimine (L²) were investigated in self‐assembly with palladium diphosphane complexes [Pd(P^P)(H₂O)₂](OTf)₂ (OTf=triflate) by using various analytical techniques, including multinuclear (¹H, ¹⁵N, and ³¹P) NMR spectroscopy and mass spectrometry (P^P=dppp, dppf, dppe; dppp=bis(diphenylphosphanyl)propane, dppf= bis(diphenylphosphanyl)ferrocene, and dppe=bis(diphenylphosphanyl)ethane). Beside the expected trimeric and tetrameric species, the interaction of an equimolar mixture of [Pd(dppp)]²⁺ ions and L¹ also generates pentameric aggregates. Due to the E/Z isomerism of L¹, a dimeric product was also observed. In all of these species, which correspond to the general formula [Pd(dppp)L¹]_n(OTf)_2n (n=2–5), the L¹ ligand is coordinated to the Pd center only through the terminal pyridyl groups. Introduction of a second equivalent of the [Pd(dppp)]²⁺ tecton results in coordination to the internal, sterically more encumbered chelating site and induces enhancement of the higher nuclearity components. The presence of higher‐order aggregates (n=5, 6), which were unexpected for the interaction of cis‐protected palladium corners with linear ditopic bridging ligands, has been demonstrated both by mass‐spectrometric and DOSY NMR spectroscopic analysis. The sequential coordination of the [Pd(dppp)]²⁺ ion is attributed to the dissimilar steric properties of the two coordination sites. In the self‐assembled species formed in a 1:1:1 mixture of [Pd(dppp)]²⁺/[Pd(dppe)]²⁺/L¹, the sterically more demanding [Pd(dppp)]²⁺ tectons are attached selectively to the pyridyl groups, whereas the more hindered imino nitrogen atoms coordinate the less bulky dppe complexes, thus resulting in a sterically directed, size‐selective sorting of the metal tectons. The propensity of the new ligands to incorporate hydrogen‐bonded solvent molecules at the chelating site was confirmed by X‐ray diffraction studies.     

Electrospray mass spectrometry and molecular modeling study of formation and stability of silver complexes with diazaperylene and bisisoquinoline

The complex formation of the following diazaperylene ligands (L) 1,12‐diazaperylene 1 , 1,1′‐bisisoquinoline 2 , 2,11‐disubstituted 1,12‐diazaperylenes (alkyl = methyl, ethyl, isopropyl, 3 , 5 , 7 ), 3,3′‐disubstituted 1,1′‐bisisoquinoline (alkyl = methyl, ethyl, isopropyl, 4 , 6 , 8 and with R = phenyl, 11 and with pyridine 12 ), and the 5,8‐dimethoxy‐substituted diazaperylene 9 , 6,6′‐dimethoxy‐substituted bisisoquinoline 10 with AgBF4 was investigated. Collision‐induced dissociation measurements were used to evaluate the relative stabilities of the ligands themselves and for the [1:1]⁺ complexes as well as for the homoleptic and heteroleptic silver [1:2]⁺ complexes in the gas phase. This method is very useful in rapid screening of the stabilities of new complexes in the gas phase. The influence of the spatial arrangement of the ligands and the type of substituents employed for the complexation were examined. The effect of the preorganization of the diazaperylene on the threshold activation voltages and thus of the relative binding energies of the different complexes are discussed. Density functional theory calculations were used to calculate the optimized structures of the silver complexes and compared with the stabilities of the complexes in the gas phase for the first time.     

Iridium(III) Complexes with Sulfonyl and Fluorine Substituents: Synthesis,Stereochemistry and Effect of Functionalisation on their Photophysical Properties

The synthesis and photophysical and electrochemical characterisation of new heteroleptic iridium complexes with electron‐withdrawing sulfonyl groups and fluorine atoms bound to phenylpyridine ligands are reported. The emission energy of these materials strongly depends on the position of the sulfonyl groups and on the number of fluorine substituents. A 90 nm wide tuning range of photoluminescence from the blue‐green (λ_em=468 nm) of iridium(III)bis[2‐(4′‐benzylsulfonyl)phenylpyridinato‐N,C2′][3‐(pentafluorophenyl)‐pyridin‐2‐yl‐1,2,4‐triazolate] to the orange (λ_em=558 nm) of iridium(III)bis[2‐(3′‐benzylsulfonyl)phenylpyridinato‐N,C2′](2,4‐decanedionate) has been achieved. Emission quantum yields ranging from 47 to 71 % have also been found for degassed solutions of the complexes, and a surprisingly high value of 16 % was recorded for iridium(III)bis[2‐(5′‐benzylsulfonyl‐3′,6′‐difluoro)phenylpyridinato‐N,C2′](2,4‐decanedionate) in air‐equilibrated dichloromethane. A unusual stereochemistry of the benzylsulfonyl‐substituted dimer and heteroleptic complexes has been detected by ¹H NMR spectroscopy, and is characterised by the mutual cis disposition of the pyridyl nitrogen atoms of the phenylpyridine ligands, which differs from the most common trans arrangement reported in the literature.     

Chloro(η6‐p‐cymene)(phosphoramidite)ruthenium(II), a 16‐Electron Fragment Stabilized by an η2‐Aryl–Metal Interaction,and Its Use in Asymmetric Cyclopropanation

Chloride abstraction from the half‐sandwich complexes [RuCl₂(η⁶‐p‐cymene)(P*‐κP)] ( 2a : P* = (S_a,R,R)‐ 1a = (1S_a)‐[1,1′‐binaphthalene]‐2,2′‐diyl bis[(1R)‐1‐phenylethyl)]phosphoramidite; 2b : P* = (S_a,R,R)‐ 1b = (1S_a)‐[1,1′‐binaphthalene]‐2,2′‐diyl bis[(1R)‐(1‐(1‐naphthalen‐1‐yl)ethyl]phosphoramidite) with (Et₃O)[PF₆] or Tl[PF₆] gives the cationic, 18‐electron complexes dichloro(η⁶‐p‐cymene){(1S_a)‐[1,1′‐binaphthalene]‐2,2′‐diyl {(1R)‐1‐[(1,2‐η)‐phenyl]ethyl}[(1R)‐1‐phenylethyl]phosphoramidite‐κP}ruthenium(II) hexafluorophosphate ( 3a ) and [Ru(S)]‐dichloro(η⁶‐p‐cymene){(1S_a)‐[1,1′‐binaphthalene]‐2,2′‐diyl {(1R)‐1‐[(1,2‐η)‐naphthalen‐1‐yl]ethyl}[(1R)‐1‐(naphthalen‐1‐yl)ethyl]phosphoramidite‐κP)ruthenium(II) hexafluorophosphate ( 3b ), which feature the η²‐coordination of one aryl substituent of the phosphoramidite ligand, as indicated by ¹H‐, ¹³C‐, and ³¹P‐NMR spectroscopy and confirmed by an X‐ray study of 3b . Additionally, the dissociation of p‐cymene from 2a and 3a gives dichloro{(1S_a)‐[1,1′‐binaphthalene]‐2,2′‐diyl [(1R)‐(1‐(η⁶‐phenyl)ethyl][(1R)‐1‐phenylethyl]phosphoramidite‐κP)ruthenium(II) ( 4a ) and di‐μ‐chlorobis{(1S_a)‐[1,1′‐binaphthalene]‐2,2′‐diyl [(1R)‐1‐(η⁶‐phenyl)ethyl][(1R)‐1‐phenylethyl]phosphoramidite‐κP}diruthenium(II) bis(hexafluorophosphate) ( 5a ), respectively, in which one phenyl group of the N‐substituents is η⁶‐coordinated to the Ru‐center. Complexes 3a and 3b catalyze the asymmetric cyclopropanation of α‐methylstyrene with ethyl diazoacetate with up to 86 and 87% ee for the cis‐ and the trans‐isomers, respectively.     

Monomeric Magnesium and Calcium Complexes containing the Rigid,Dianionic 1, 2‐Bis[(2, 5‐di‐tert‐butylphenyl)imino]acenaphthene (dtb‐BIAN) and 1, 2‐Bis[(2‐biphenyl)imino]acenaphthene (bph‐BIAN) Ligands

The new rigid bidentate nitrogen ligands 1, 2‐bis[(2, 5‐di‐tert‐butylphenyl)imino]acenaphthene ( 1 ) (dtb‐BIAN) and 1, 2‐bis[(2‐biphenyl)imino]acenaphthene ( 2 ) (bph‐BIAN) have been synthesized by condensation of 1, 2‐acenaphthylenedione with 2, 5‐di‐tert‐butylaniline and 2‐aminobiphenyl, respectively. Reduction of 1 and 2 with magnesium and calcium results in the formation of the monomeric metal complexes [(dtb‐BIAN)Mg(THF)₂] ( 3 ), [(bph‐BIAN)Mg(DME)₂] ( 4 ), and [(bph‐BIAN)Ca(THF)₃] ( 5 ). Compounds 1 — 5 have been characterized by C/H analyses, IR, ¹H NMR, and ¹³C NMR spectra, the structures of 2 , 3 , and 5 have been estimated by single crystal X‐ray diffraction.     

Synthesis of Some Novel bis‐Spiro[indole‐pyrazolinyl‐thiazolidine]‐2,4′‐diones

The reaction of 1H‐indol‐2,3‐diones with 1,6‐dibromohexane has resulted in the formation of new 1H‐indol‐2,3‐diones‐1,1′‐(1,6‐hexanediyl)bis in quantitative yields. These compounds have been used for the synthesis of novel [3′‐(2,3‐dimethyl‐5‐oxo‐1‐phenyl‐3‐pyrazolin‐4‐yl)spiro[3H‐indol‐3,2′‐thiazolidine]‐2,4′‐dione]‐1,1′‐(1,6‐hexanediyl)bis via bis Schiff's bases, [3‐(2,3‐dimethyl‐5‐oxo‐1‐phenyl‐3‐pyrazolin‐4‐yl) imino‐1H‐indol‐2‐one]‐1,1′‐(1,6‐hexanediyl)bis.     

Three Transition Metal(II) Coordination Polymers Constructed by a Semi‐rigid Bis‐pyridyl‐bis‐amide and Dicarboxylates Mixed Ligands: Assembly,Structures and Properties

Three coordination polymers, namely [Co(BDC)( L )] · H₂O ( 1 ), [Co(NPH)( L )] · H₂O ( 2 ), and [Ni(NPH)( L )(H₂O)₃] · H₂O ( 3 ) [H₂BDC = 1, 3‐benzenedicarboxylic acid, H₂NPH = 3‐nitrophthalic acid, L = N,N′‐bis(3‐pyridyl)‐terephthalamide] were hydrothermally synthesized by self‐assembly of cobalt/nickel chloride with a semi‐rigid bis‐pyridyl‐bis‐amide ligand and two aromatic dicarboxylic acids. Single crystal X‐ray diffraction analyses revealed that complexes 1 and 2 are two‐dimensional (2D) coordination polymers containing a one‐dimensional (1D) ribbon‐like Co‐dicarboxylate chain and a 1D zigzag Co‐ L chain. Although the coordination numbers of Co^II ions and the coordination modes of two dicarboxylates are different in complexes 1 and 2 , they have a similar 3, 5‐connected {4².6⁷.8}{4².6} topology. In complex 3 , the adjacent Ni^II ions are linked by L ligands to form a 1D polymeric chain, whereas the 1D chains does not extend into a higher‐dimensional structure due to the ligand NPH with monodentate coordination mode. The adjacent layers of complexes 1 and 2 and the adjacent chains of 3 are further linked by hydrogen bonding interactions to form 3D supramolecular networks. Moreover, the thermal stabilities, fluorescent properties, and photocatalytic activities of complexes 1 – 3 were studied.     

Synthesis,cytotoxicity and anti‐metastatic properties of new pyridyl–thiazole arene ruthenium(II) complexes

A series of novel ruthenium(II)–cymene complexes ( 1 – 8 ) containing substituted pyridyl–thiazole ligands, [Ru(η⁶‐p‐cymene)(L)Cl]Cl (L = N,N‐chelating derivatives), have been synthesized and characterized using elemental analysis, infrared, ¹H NMR and ¹³C NMR spectroscopies and mass spectrometry. All these complexes not only display marked cytotoxicity in vitro against three different human cancer cell lines (HeLa, A549 and MDA‐MB‐231), but also exhibit promising anti‐metastatic activity at sub‐cytotoxic concentrations. Cell cycle analysis shows that the ruthenium(II) complex‐induced growth inhibition was mainly caused by S‐phase cell cycle arrest. Further protein level analysis suggests that compound 5 may exert antitumor activity via a p53‐independent mechanism.     

Tin(II) Halide Insertion or Halogen Exchange in the Reactions of Dihaloplatinum(II) Complexes with Tin(II) Halide

Reactions of SnCl₂ with the complexes cis‐[PtCl₂(P₂)] (P₂=dppf (1,1′‐bis(diphenylphosphino)ferrocene), dppp (1,3‐bis(diphenylphosphino)propane=1,1′‐(propane‐1,3‐diyl)bis[1,1‐diphenylphosphine]), dppb (1,4‐bis(diphenylphosphino)butane=1,1′‐(butane‐1,4‐diyl)bis[1,1‐diphenylphosphine]), and dpppe (1,5‐bis(diphenylphosphino)pentane=1,1′‐(pentane‐1,5‐diyl)bis[1,1‐diphenylphosphine])) resulted in the insertion of SnCl₂ into the Pt? Cl bond to afford the cis‐[PtCl(SnCl₃)(P₂)] complexes. However, the reaction of the complexes cis‐[PtCl₂(P₂)] (P₂=dppf, dppm (bis(diphenylphosphino)methane=1,1′‐methylenebis[1,1‐diphenylphosphine]), dppe (1,2‐bis(diphenylphosphino)ethane=1,1′‐(ethane‐1,2‐diyl)bis[1,1‐diphenylphosphine]), dppp, dppb, and dpppe; P=Ph₃P and (MeO)₃P) with SnX₂ (X=Br or I) resulted in the halogen exchange to yield the complexes [PtX₂(P₂)]. In contrast, treatment of cis‐[PtBr₂(dppm)] with SnBr₂ resulted in the insertion of SnBr₂ into the Pt? Br bond to form cis‐[Pt(SnBr₃)₂(dppm)], and this product was in equilibrium with the starting complex cis‐[PtBr₂(dppm)]. Moreover, the reaction of cis‐[PtCl₂(dppb)] with a mixture SnCl₂/SnI₂ in a 2 : 1 mol ratio resulted in the formation of cis‐[PtI₂(dppb)] as a consequence of the selective halogen‐exchange reaction. ³¹P‐NMR Data for all complexes are reported, and a correlation between the chemical shifts and the coupling constants was established for mono‐ and bis(trichlorostannyl)platinum complexes. The effect of the alkane chain length of the ligand and Sn^II halide is described.