One‐Dimensional Ferromagnetically Coupled Bimetallic Chains Constructed with trans‐[Ru(acac)2(CN)2]−: Syntheses,Structures, Magnetic Properties,and Density Functional Theoretical Study

Four cyano‐bridged 1D bimetallic polymers have been prepared by using the paramagnetic building block trans‐[Ru(acac)₂(CN)₂]^? (Hacac=acetylacetone): {[{Ni(tren)}{Ru(acac)₂(CN)₂}][ClO₄]?CH₃OH}_n ( 1 ) (tren=tris(2‐aminoethyl)amine), {[{Ni(cyclen)}{Ru(acac)₂(CN)₂}][ClO₄]? CH₃OH}_n ( 2 ) (cyclen=1,4,7,10‐tetraazacyclododecane), {[{Fe(salen)}{Ru(acac)₂(CN)₂}]}_n ( 3 ) (salen^2?=N,N′‐bis(salicylidene)‐o‐ethyldiamine dianion) and [{Mn(5,5′‐Me₂salen)}₂{Ru(acac)₂(CN)₂}][Ru(acac)₂(CN)₂]? 2 CH₃OH ( 4 ) (5,5′‐Me₂salen=N,N′‐bis(5,5′‐dimethylsalicylidene)‐o‐ethylenediimine). Compounds 1 and 2 are 1D, zigzagged NiRu chains that exhibit ferromagnetic coupling between Ni^II and Ru^III ions through cyano bridges with J=+1.92 cm^?1, z J′=?1.37 cm^?1, g=2.20 for 1 and J=+0.85 cm^?1, z J′=?0.16 cm^?1, g=2.24 for 2 . Compound 3 has a 1D linear chain structure that exhibits intrachain ferromagnetic coupling (J=+0.62 cm^?1, z J′=?0.09 cm^?1, g=2.08), but antiferromagnetic coupling occurs between FeRu chains, leading to metamagnetic behavior with T_N=2.6 K. In compound 4 , two Mn^III ions are coordinated to trans‐[Ru(acac)₂(CN)₂]^? to form trinuclear Mn₂Ru units, which are linked together by π–π stacking and weak Mn???O* interactions to form a 1D chain. Compound 4 shows slow magnetic relaxation below 3.0 K with ?=0.25, characteristic of superparamagnetic behavior. The Mn^III???Ru^III coupling constant (through cyano bridges) and the Mn^III???Mn^III coupling constant (between the trimers) are +0.87 and +0.24 cm^?1, respectively. Compound 4 is a novel single‐chain magnet built from Mn₂Ru trimers through noncovalent interactions. Density functional theory (DFT) combined with the broken symmetry state method was used to calculate the molecular magnetic orbitals and the magnetic exchange interactions between Ru^III and M (M=Ni^II, Fe^III, and Mn^III) ions. To explain the somewhat unexpected ferromagnetic coupling between low‐spin Ru^III and high‐spin Fe^III and Mn^III ions in compounds 3 and 4 , respectively, it is proposed that apart from the relative symmetries, the relative energies of the magnetic orbitals may also be important in determining the overall magnetic coupling in these bimetallic assemblies.     

Solvent‐Mediated Functionalization of Benzofuroxan on Electron‐Rich Ruthenium Complex Platform

An unprecedented reactivity profile of biochemically relevant R‐benzofuroxan (R=H, Me, Cl), with high structural diversity and molecular complexity on a selective {Ru(acac)₂} (acac=acetylacetonate) platform, in conjugation with EtOH solvent mediation, is revealed. This led to the development of monomeric [Ru^III(acac)₂(L^1R)] ( 1 a – 1 c ; L^1R=2‐nitrosoanilido derivatives) and dimeric [{Ru^II(acac)₂}₂(L^2R)] ( 2 a – 2 b ; L^2R=(1E,2E)‐N¹,N²‐bis(2‐nitrosophenyl)ethane‐1,2‐diimine derivatives) complexes in one pot with a change in the metal redox conditions. The functionalization of benzofuroxan in 1 and 2 implied in situ reduction of N=O to NH^? in the former and solvent‐assisted multiple N?C coupling in the latter. The aforesaid transformation processes were authenticated through structural elucidation of representative complexes, and evaluated by their spectroscopic/electrochemical features, along with C₂D₅OD labeling and monitoring of the impact of substituents (R) in the benzofuroxan framework on the product distribution process. The noninnocent potential of newly developed L¹ and L² in 1 and 2 , respectively, was also probed by spectroelectrochemistry in combination with DFT calculations.     

Zirconium‐chelate and mono‐η‐ cyclopentadienyl zirconium‐chelate/ methylalumoxane systems as soluble Ziegler–Natta olefin polymerization catalysts

Zirconium‐chelate and mono‐η‐cyclopentadienyl zirconium‐chelate complexes were tested as ethene and propene polymerization catalysts in combination with methylalumoxane (MAO) as a co‐catalyst: in particular (acac) _nZrCl_4−n (1a–c) (acac = acetylacetonato), (dbm) _nZrCl_4−n (2a–2c) (dbm = dibenzoylmethanato = 1,3‐diphenylpropanedionato) (n = 2–4) and (dbm)₂ZrCl₂(thf) (3) (thf = tetrahydrofuran), (η‐C₅H₅)[H₂B (C₃H₃N₂)₂]ZrCl₂ (4), (η‐C₅H₅)[HB (C₃H₃N₂)₃] ZrCl₂ (5) and (η‐C₅H₅)[(Me₃SiN)₂ CPh]ZrCl₂ (6). Polymerization productivities comparable with the (η‐C₅H₅)₂ZrCl₂ reference system were observed towards ethene for all of the above complexes. In addition, compound 6 showed some minor polymerization activity towards propene. Ethylalumoxane or isobutylalumoxane did not exhibit a co‐catalytic activity for these chelate complexes; in combination with MAO these higher alumoxanes were even found to be deactivating ⁹¹Zr NMR data are reported for 1b, 1c, 4 and 5. Copyright © 2000 John Wiley & Sons, Ltd.     

Gas‐phase ligand exchange of select transition‐metal acetylacetonate and hexafluoroacetylacetonate complexes

Gas‐phase ligand exchange reactions between M(acac)₂ and M(hfac)₂ species, where M is Cu(II) and/or Ni(II), were observed to occur in a double‐focusing reverse‐geometry magnetic sector mass spectrometer. The gas‐phase mixed ligand product, [M(acac)(hfac)]⁺, was formed following the co‐sublimation of either homo‐metal or hetero‐metal precursors. The gas‐phase formation of [Cu(acac)(hfac)]⁺ from hetero‐metal precursors is reported herein for the first time. The [Ni(acac)(hfac)]⁺ complex is also observed for the first time to form following the co‐sublimation of not only Ni precursors, but also from separate Ni and Cu precursors. The corresponding fragmentation patterns of these species are also presented, and the mixed metal mixed ligand product [NiCu(acac)₂(hfac)]⁺ is observed. Copyright © 2008 John Wiley & Sons, Ltd.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 58. Zur Kenntnis von 2-(Dimethylaminomethyl)ferrocenyl-Verbindungen des Vanadiums,Molybdäns,Wolframs, Thoriums und Urans

Contributions to the Chemistry of Transition Metal Alkyl Compounds. 58 On 2-(Dimethylaminomethyl)ferrocenyl Compounds of Vanadium, Molybdenum, Tungsten, Thorium, and Uranium Earlier results according to which dimethylaminomethylferrocenyl groups (FcN) are able to form stable organometallic chelate compounds were confirmed by synthesis of the heterobimetallic chelate compounds (FcN)₂VO · Li(acac) II , (FcN)MoO₂(acac) III , (FcN)WOCl₃ IV , (FcN)Th(acac)₃ V , and (FcN)UO₂(acac) VI from the corresponding metal acetylacetonates or oxidchlorides and (FcN)Li I . The new compounds were characterized by elemental analysis, the i.r., ¹H-n.m.r., and electron spectra and by their effective magnetic moments.     

Organo‐Palladium(II)‐Verbindungen mit PdC4‐Koordination: Phenylethinyl‐ und Methylphenylethinylkomplexe

Tetrakis(p‐tolyl)oxalamidinato‐bis[acetylacetonatopalladium(II)] ([Pd₂(acac)₂(oxam)]) reacted with Li–C≡C–C₆H₅ in THF with formation of [Pd(C≡C–C₆H₅)₄Li₂(thf)₄] ( 1a ). Reaction of [Pd₂(acac)₂(oxam)] with a mixture of 6 equiv. Li–C≡C–C₆H₅ and 2 equiv. LiCH₃ resulted in the formation of [Pd(CH₃)(C≡C–C₆H₅)₃Li₂(thf)₄] ( 2 ), and the dimeric complex [Pd₂(CH₃)₄(C≡C–C₆H₅)₄Li₄(thf)₆] ( 3 ) was isolated upon reaction of [Pd₂(acac)₂(oxam)] with a mixture of 4 equiv. Li–C≡C–C₆H₅ and 4 equiv. LiCH₃. 1 – 3 are extremely reactive compounds, which were isolated as white needles in good yields (60–90%). They were fully characterized by IR, ¹H‐, ¹³C‐, ⁷Li‐NMR spectroscopy, and by X‐ray crystallography of single crystals. In these compounds Li ions are bonded to the two carbon atoms of the alkinyl ligand. 1a reacted with Pd(PPh₃)₄ in the presence of oxygen to form the already known complexes trans‐[Pd(C≡C–C₆H₅)₂(PPh₃)₂] and [Pd(η²‐O₂)(PPh₃)₂]. In addition, 1a is an active catalyst for the Heck coupling reaction, but less active in the catalytic Sonogashira reaction.     

New 3‐Imidazoline Derivatives and their Palladium(II) Complexes

The protection of the hydroxy group of 1‐hydroxy‐2.2.4.5.5‐pentamethyl‐3‐imidazoline by a t‐butyldimethylsilyl group gives the silane 1 which allows via the 4‐lithium salt the preparation of 4‐substituted derivatives, i. e. a dithiocarboxylic acid ( 2 ), a disulfide ( 3 ), a phosphane ( 4 ) and a thioether ( 5 ). Oxidation of 4‐lithiated 1 yields under C–C coupling an ethylene bridged bis(3‐imidazoline) ( 6 ). From these compounds Pd(II) and Pt(II) complexes M( 4 )₂Cl₂ (M = Pd, Pt and Pd( 5 )Cl₂ were prepared and the structure of the dithiocarboxylate chelate complex Pd( 2 ‐H⁺)₂ ( 7 ) was determined by X‐ray diffraction. Cleavage of the silyl group from 7 gives complex 8 which can be oxidized to the corresponding diradical ( 9 ). Complex 9 was characterized by its EPR spectrum. Measurements of the magnetic susceptibility of 9 reveal strong antiferromagnetic coupling between the two spins at low temperatures.     

DFT and TD‐DFT study of iridium complexes with low‐color‐temperature and low‐efficiency roll‐off properties

A series of heteroleptic cyclometalated Ir (III) complexes with low‐color‐temperature and low‐efficiency roll‐off properties, which cause a fast reduction in efficiency when the drive current increases, for organic light‐emitting devices are investigated theoretically to explore their electronic structures and spectroscopic properties. The geometries, electronic structures, lowest‐lying singlet absorptions and triplet emissions of (ptpy)₂Ir(acac), and the theoretically designed models (ptpy)₂Ir(tpip), (F‐ptpy)₂Ir(acac), (F‐ptpy)₂Ir(tpip), (F₂‐ptpy)₂Ir(acac) and (F₂‐ptpy)₂Ir(tpip), are investigated with density functional theory approaches, where ptpy denotes 4‐phenylthieno [3,2‐c] pyridine, acac denotes acetylacetonate, tpip denotes tetraphenylimido‐diphosphinate, F‐ptpy denotes 4‐(3‐fluorophenyl) thieno [3,2‐c] pyridine, and F₂‐ptpy denotes 4‐(2,4‐difluorophenyl) thieno [3,2‐c] pyridine.     

D‐Glucosamine in iron‐catalysed cross‐coupling reactions of Grignards with allylic and vinylic bromides: application to the synthesis of a key sitagliptin precursor

A sustainable D ‐glucosamine ligand is successfully introduced into iron‐catalysed C ? C cross‐coupling reactions for the first time. The Fe(acac)₂/D ‐glucosamine·HCl/Et₃N catalytic system was effective at 5 mol% loading in coupling reactions of Grignard reagents with organic bromides. Moderate to high efficiency was achieved with preserved stereochemistry when allyl (Csp³) or alkenyl (Csp²) bromides were coupled with phenylmagnesium (Csp²) or benzylmagnesium (Csp³) bromides. The catalytic system developed was also successfully applied for the novel and economic preparation of a Michael‐acceptor‐like starting material used in an alternative synthesis of the drug sitagliptin, a known blockbuster for the treatment of type II diabetes mellitus. Copyright © 2015 John Wiley & Sons, Ltd.     

MnFe2O4 nanoclusters as labels for the quantitative detection of D‐dimer in a lateral‐flow immunochromatographic assay

In this study, MnFe₂O₄ nanoclusters were prepared as bioprobes to establish a lateral‐flow immunochromatographic assay (LFIA) for the rapid and quantitative detection of D‐dimer for the first time. The magnetic properties of the magnetic labels play a key role in the quantitative detection of biomolecules. The 47.3‐nm MnFe₂O₄ magnetic nanoclusters (MNCs) with good dispersion and high saturation magnetization (76 emu/g) were fabricated via thermal decomposition of Fe(acac)₃ with Mn(acac)₂. The prepared MnFe₂O₄ MNCs were well dispersed in water because the surfaces were fully covered with 3,4‐dihydroxyhydrocinnamic acid (DHCA) molecules by ligand exchange. Anti‐D‐dimer antibodies were coupled on the surface of MnFe₂O₄ MNCs, and the target protein, D‐dimer, was detected, in the range 0.05–6 μg/mL. This assay provides a promising platform for D‐dimer detection for point‐of‐care diagnosis.     

Radical Cyclization of Alkene‐Tethered Ketones Initiated by Hydrogen‐Atom Transfer

An unprecedented C?C coupling reaction between alkenes and ketones by hydrogen‐atom transfer, using Fe(acac)₃ and PhSiH₃ in EtOH, is described. This mild protocol features high site selectivity and allows the construction of sterically congested structures containing tertiary alcohols and quaternary centers. The overall process introduces a novel strategic bond disconnection for ring‐closing reactions.     

Solid,Solution, and Theoretical Approach of [Cu(CN‐acac)(dmeen)]+

The reaction of bis(3‐cyano‐2,4‐pentanedionato)copper(II), [Cu(NC‐acac)₂] with the nitrogenous base N,N‐dimethyl, N′‐ethyl‐1,2‐ethylenediamine (dmeen) in the presence of Cu(ClO₄)₂ · 6H₂O, afforded a new cationic mixed‐ligand chelate [Cu(CN‐acac)(dmeen)]⁺. Its structure was characterized spectroscopically (IR, UV/Vis, EPR) and verified by X‐ray diffraction studies as [Cu(CN‐acac)(dmeen)(H₂O)]ClO₄. The coordination of CN‐acac^– as bridging ligand leads to a polymeric helical chain, which extends in the crystallographic c axis. Density functional theory (DFT) calculations suggest that in the solid state the anion CN‐acac^– binding is envisaged through the nitrogen atom of the cyanido group, establishing an octahedral arrangement around copper, whereas in solution, the square‐planar arrangement is prevailed, in accordance with the EPR findings.     

Ate Complexes in Iron‐Catalyzed Cross‐Coupling Reactions

Iron‐catalyzed cross‐coupling reactions have an outstanding potential for sustainable organic synthesis, but remain poorly understood mechanistically. Here, we use electrospray‐ionization (ESI) mass spectrometry to identify the ionic species formed in these reactions and characterize their reactivity. Transmetalation of Fe(acac)₃ (acac=acetylacetonato) with PhMgCl in THF (tetrahydrofuran) produces anionic iron ate complexes, whose nuclearity (1 to 4 Fe centers) and oxidation states (ranging from ?I to +III) crucially depend on the presence of additives or ligands. Upon addition of iPrCl, formation of the heteroleptic Fe^III complex [Ph₃Fe(iPr)]^? is observed. Gas‐phase fragmentation of this complex results in reductive elimination and release of the cross‐coupling product with high selectivity.     

Cobalt(II) acetylacetonate complex immobilized on aminosilane‐modified SBA‐15 as an efficient catalyst for epoxidation of trans‐stilbene with molecular oxygen

From environmental and economic points of view, it is highly desirable to develop a clean and efficient catalytic process to produce epoxides. An attractive approach is to use a solid, recyclable catalyst and molecular oxygen as the oxidant without any sacrificial reductant or other additives. Nonetheless, the catalysts reported up to now still cannot balance catalytic activity with epoxide selectivity. It is of great importance to explore novel catalysts with both high activity and selectivity for the epoxidation of olefins. In this work, cobalt(II) acetylacetonate (Co(acac)₂) was covalently bonded to the silica surface of SBA‐15 molecular sieve by multi‐step grafting using 3‐aminopropytrimethoxysilane (APTS) as coupling agent. Characterizations with nitrogen physisorption, X‐ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy and thermogravimetric analysis suggested that the metal complex was successfully immobilized on the aminosilane‐modified SBA‐15 surface and the channel structure remained intact. The synthesized Co(acac)₂APTS@SBA‐15 catalyst was used in the epoxidation of trans‐stilbene (TS) with molecular oxygen. Compared to the sample prepared by the impregnation method as well as Co(acac)₂ solutions under the same reaction conditions, the Co(acac)₂ immobilized catalyst exhibited remarkably higher TS conversion and trans‐stilbene oxide (TSO) selectivity. An increase in TS conversion with Co content was observed when the Co loading was lower than 0.70% and the 0.70Co(acac)₂APTS@SBA‐15 sample exhibited the best catalytic performance. Up to 50.1% of TS conversion could be achieved within 6 h, affording TSO selectivity as high as 96.7%. The superior catalytic performance of this particular catalyst is attributed to the high activity of the immobilized Co(acac)₂ species on SBA‐15. Copyright © 2016 John Wiley & Sons, Ltd.     

Vapochromic Ionic Liquids from Metal–Chelate Complexes Exhibiting Reversible Changes in Color,Thermal, and Magnetic Properties

Vapor‐ and gas‐responsive ionic liquids (ILs) comprised of cationic metal‐chelate complexes and bis(trifluoromethanesulfonyl)imide (Tf₂N) have been prepared, namely, [Cu(acac)(BuMe₃en)][Tf₂N] ( 1 a ), [Cu(Bu‐acac)(BuMe₃en)][Tf₂N] ( 1 b ), [Cu(C₁₂‐acac)(Me₄en)][Tf₂N] ( 1 c ), [Cu(acac)(Me₄en)][Tf₂N] ( 1 d ), and [Ni(acac)(BuMe₃en)][Tf₂N] ( 2 a ) (acac=acetylacetonate, Bu‐acac=3‐butyl‐2,4‐pentanedionate, C₁₂‐acac=3‐dodecyl‐2,4‐pentanedionate, BuMe₃en=N‐butyl‐N,N′,N′‐tetramethylethylenediamine, and Me₄en=N,N,N′,N′‐trimethylethylenediamine). These ILs exhibited reversible changes in color, thermal properties, and magnetic properties in response to organic vapors and gases. The Cu^II‐containing ILs are purple and turn blue‐purple to green when exposed to organic vapors, such as acetonitrile, methanol, and DMSO, or ammonia gas. The color change is based on the coordination of the vapor molecules to the cation, and the resultant colors depend on the coordination strength (donor number, DN) of the vapor molecules. The vapor absorption caused changes in the melting points and viscosities, leading to alteration in the phase behaviors. The IL with a long alkyl chain ( 1 d ) transitioned from a purple solid to a brown liquid at its melting point. The Ni^II‐containing IL ( 2 a ) is a dark red diamagnetic liquid, which turned into a green paramagnetic liquid by absorbing vapors with high DN. Based on the equilibrium shift from four‐ to six‐coordinated species, the liquid exhibited thermochromism and temperature‐dependent magnetic susceptibility after absorbing methanol.     

Fabrication of covalently functionalized mesoporous silica core–shell magnetite nanoparticles with palladium(II) acetylacetonate: application as a magnetically separable nanocatalyst for Suzuki cross‐coupling reaction of acyl halides with boronic acids

We report the preparation of supported palladium(II) acetylacetonate, Pd(acac)₂, coordinated by pendant acac groups, by reacting palladium acetate with acac‐functionalized doubly silica‐coated magnetic nanoparticles. The solid support consists of an amorphous silica‐coated (as magnetite protecting layer) magnetite core and a mesoporous silica shell. The magnetically separable palladium nanocatalyst is active for Suzuki cross‐coupling reaction of acyl halides with boronic acids. The catalyst is simply isolated from the reaction mixture that allows fast and efficient isolation of product and catalyst compared to traditional methods that generally make use of time‐ and solvent‐consuming procedures. Copyright © 2015 John Wiley & Sons, Ltd.     

Redox Non‐Innocence and Isomer‐Specific Oxidative Functionalization of Ruthenium‐Coordinated β‐Ketoiminate

This article deals with isomeric ruthenium complexes [Ru^III(L^R)₂(acac)] (S=1/2) involving unsymmetric β‐ketoiminates (AcNac) (L^R=R‐AcNac, R=H ( 1 ), Cl ( 2 ), OMe ( 3 ); acac=acetylacetonate) [R=para‐substituents (H, Cl, OMe) of N‐bearing aryl group]. The isomeric identities of the complexes, cct (cis‐cis‐trans, blue, a ), ctc (cis‐trans‐cis, green, b ) and ccc (cis‐cis‐cis_, pink, c ) with respect to oxygen (acac), oxygen (L) and nitrogen (L) donors, respectively, were authenticated by their single‐crystal X‐ray structures and spectroscopic/electrochemical features. One‐electron reversible oxidation and reduction processes of 1 – 3 led to the electronic formulations of [Ru^III(L)(L ^? )(acac)]⁺ and [Ru^II(L)₂(acac)]^? for 1 ⁺‐ 3 ⁺ (S=1) and 1^? – 3^? (S=0), respectively. The triplet state of 1 ⁺‐ 3 ⁺ was corroborated by its forbidden weak half‐field signal near g≈4.0 at 4 K, revealing the non‐innocent feature of L. Interestingly, among the three isomeric forms ( a – c in 1 – 3 ), the ctc ( b in 2 b or 3 b ) isomer selectively underwent oxidative functionalization at the central β‐carbon (C?H→C=O) of one of the L ligands in air, leading to the formation of diamagnetic [Ru^II(L)(L ′ )(acac)] (L ′ =diketoimine) in 4 / 4′ . Mechanistic aspects of the oxygenation process of AcNac in 2 b were also explored via kinetic and theoretical studies.     

Bis(μ‐2‐{5‐[(pyridin‐4‐ylmethyl)sulfanyl]‐1,3,4‐oxadiazol‐2‐yl}phenolato)bis[(acetylacetonato)copper(II)]: a novel binuclear metallocycle

The new asymmetric ligand 2‐{5‐[(pyridin‐4‐ylmethyl)sulfanyl]‐1,3,4‐oxadiazol‐3‐yl}phenol (HL) has been used to synthesize the novel discrete title binuclear metallocycle, [Cu₂(C₁₄H₁₀N₃O₂S)₂(C₅H₇O₂)₂] or Cu₂L₂(acac)₂ (acac is acetylacetonate). Each Cu^II centre is five‐coordinate and adopts a square‐pyramidal geometry. Two ligands are connected by two Cu^II cations to form the dinuclear metallocycle, which lies across a crystallographic inversion centre. Discrete molecules are linked into a two‐dimensional structure through weak Cu...S, C—H...π and π–π interactions.     

Syntheses,and Crystal Structures of Indium Complexes with η2‐Piperidinyldithiocarbamate and η2‐Pyridine‐2‐Thionate Containing Ligands: Structures of [In(η2‐S2CNC5H10)3] and [In(η2‐pyS)3]

The η²‐thio‐indium complexes [In(η²‐thio)₃] (thio = S₂CNC₅H₁₀, 2 ; SNC₄H₄, (pyridine‐2‐thionate, pyS, 3 ) and [In(η²‐pyS)₂(η²‐acac)], 4 , (acac: acetylacetonate) are prepared by reacting the tris(η²‐acac)indium complex [In(η²‐acac)₃], 1 with HS₂CNC₅H₁₀, pySH, and pySH with ratios of 1:3, 1:3, and 1:2 in dichloromethane at room temperature, respectively. All of these complexes are identified by spectroscopic methods and complexes 2 and 3 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 : space group, C2/c with a = 13.5489(8) Å, b = 12.1821(7) Å, c = 16.0893(10) Å, β = 101.654(1)°, V = 2600.9(3) ų, and Z = 4. The structure was refined to R = 0.033 and Rw = 0.086; Crystal data for 3 : space group, P2₁ with a = 8.8064 (6) Å, b = 11.7047 (8) Å, c = 9.4046 (7) Å, β = 114.78 (1)°, V = 880.13(11) ų, and Z = 2. The structure was refined to R = 0.030 and Rw = 0.061. The geometry around the metal atom of the two complexes is a trigonal prismatic coordination. The piperidinyldithiocarbamate and pyridine‐2‐thionate ligands, respectively, coordinate to the indium metal center through the two sulfur atoms and one sulfur and one nitrogen atoms, respectively. The short C‐N bond length in the range of 1.322(4)–1.381(6) Å in 2 and C‐S bond length in the range of 1.715(2)–1.753(6) Å in 2 and 3 , respectively, indicate considerable partial double bond character.     

Ligandless C‐C bond formation via Suzuki–Miyaura reaction in micelles or water–ethanol solution using PdPtZn and PdZn nanoparticle thin films

PdPtZn and PdZn nanoparticle (NP) thin films were synthesized by the reduction of [PdCl₂(cod)], [PtCl₂(cod)] (cod = cis,cis‐1,5‐cyclooctadiene) and [Zn(acac)₂] (acac = acetylacetonate) complexes at an oil–water interface. The structure and morphology of the as‐prepared NPs were characterized with X‐ray diffraction, transmission electron microscopy and energy dispersive analysis of X‐rays. Catalytic activity of the prepared NPs was investigated in the Suzuki–Miyaura cross‐coupling reaction in H₂O–EtOH and various micellar media systems such as cetyltrimethylammonium bromide (cationic surfactant), sodium dodecylsulfate (anionic surfactant) and Pluronic P123 (non‐ionic surfactant). PdPtZn and PdZn thin films exhibited higher catalytic activity compared to Pd thin film in the Suzuki–Miyaura coupling reaction due to the appropriate interaction between palladium, platinum and zinc metals. Copyright © 2015 John Wiley & Sons, Ltd.