Metal Derivatives of Heterocyclic Thioamides: Synthesis and Crystal Structures of Copper Complexes with 1‐Methyl‐1,3‐imidazoline‐2‐thione and 1,3‐Imidazoline‐2‐thione

Reactions of copper(I) halides (Cl, Br, I) with 1‐methyl‐1, 3‐imidazoline‐2‐thione (mimzSH) in 1 : 2 molar ratio yielded sulfur‐bridged dinuclear [Cu₂X₂(μ‐S‐mimzSH)₂(η¹‐S‐mimzSH)₂] (X = I, 1 , Br, 2 ; Cl, 3 ) complexes. Copper(I) iodide with 1,3‐imidazoline‐2‐thione (imzSH₂) and Ph₃P in 1 : 1 : 1 molar ratio has also formed a sulfur‐bridged dinuclear [Cu₂I₂(μ‐S‐imzSH₂)₂(PPh₃)₂] ( 4 ) complex. The central Cu(μ‐S)₂Cu cores form parallelograms with unequal Cu–S bond distances {2.324(2), 2.454(3) Å} ( 1 ); {2.3118(6), 2.5098(6) Å} ( 2 ); {2.3075(4), 2.5218(4) Å} ( 3 ); {2.3711(8), 2.4473(8) Å} ( 4 ). The Cu···Cu separations, 2.759–2.877Å in complexes 1 – 3 are much shorter than 3.3446Å in complex 4 . The weak intermolecular interactions {H₂CH···S^# ( 2 ); CH···Cl^# ( 3 ); NH···I^# ( 4 )} between dimeric units in complexes 2 – 4 lead to the formation of linear 1D polymers.     

Anion Effects on the Formation of Silver(I) Complexes with the Flexible Ligand 4,4′‐Bis(1,2,4‐triazol‐1‐ylmethyl)biphenyl

The reaction of 4,4′‐bis(1,2,4‐triazol‐1‐ylmethyl)biphenyl (btmb) with silver(I) salts of BF₄^–, NO₃^– and N₃^– led to the formation of four new silver(I) coordination polymers {[Ag(btmb)]BF₄}_n ( 1 ), {[Ag₂(btmb)₃](NO₃)₂(H₂O)₅}_n ( 2 ), [Ag₂(btmb)(N₃)₂]_n ( 3 ), and [Ag(btmb)(N₃)]_n ( 4 ). Their coordination number varies from 2 (in 1 ) to 3 (in 2 ), 4 (in 3 ), and 5 (in 4 ). Different from the single chain structure of 1 , complex 2 displays a 1D ladder‐like double chain framework, whereas complex 3 exhibits a 2D layered architecture. Complex 4 has the same anion as complex 3 but shows a different metal‐to‐ligand ratio and a 1D double‐zigzag chain structure. Both 3 and 4 have Ag ··· Ag argentophilic interactions. The ligand btmb adopts both cis or trans configuration in the studied complexes. A trans‐ or cis‐btmb ligand link silver ions with Ag ··· Ag distances of ≈?18 and 13 Å, respectively. BF₄^– and NO₃^– are non‐coordinating anions in 1 and 2 . N₃^– is the bridging anion in 3 (1,3‐bridging fashion) and 4 (1,1‐bridging fashion). These findings suggest that the coordination numbers around the Ag^I ion correlate to the coordination abilities of anions and the btmb to silver ratio. In addition, the influence of anions on thermal stability were also investigated. This work is a good example that nicely supports the less explored field of anion‐dependent structures of complexes with non‐pyridyl ligands.     

Zinc(II) Tri‐tert‐butoxysilanethiolates. Synthesis,Properties, Crystal and Molecular Structures of [Zn{SSi(OBut)3}2(NH3)L] (L = 2‐Picoline or 2,4‐Lutidine) and [Zn{SSi(OBut)3}2(NH3)2] · MeCN Complexes

[Zn{SSi(OBu^t)₃}₂(NH₃)]₂ ( 1 ) reacts with 2‐picoline or 2,4‐lutidine (L) without elimination of ammonia giving stable monometallic complexes [Zn{SSi(OBu^t)₃}₂(NH₃)L] ( 3 and 4 ), with two different nitrogen ligands bonded to the metal center. Reaction of (Bu^tO)₃SiSH with zinc di(acetylacetonate) in ammonia atmosphere leads to the complex with two ammine ligands [Zn{SSi(OBu^t)₃}₂(NH₃)₂] · MeCN ( 5 ). Molecular and crystal structures of 3 , 4 and 5 have been determined by the single crystal X‐ray structural analysis. All have distorted tetrahedral geometry. The presence of ammonia gives rise to hydrogen bonds, different in all three cases. 3 , 4 , and 5 are the first examples of structurally characterized ammine ligated zinc thiolates.     

Synthesis,Characterization, and Luminescent Properties of Silver(I) Complexes based on Diphosphine Ligands and 6,7‐Dicyanodipyridoquinoxaline

Five mono‐nuclear silver (I) complexes with 6,7‐dicyanodipyridoquinoxaline ligand, namely {[Ag(DPEphos)(dicnq)]NO₃}₂ · CH₃OH ( 1 ), [Ag(DPEphos)(dicnq)]BF₄ · CH₃OH ( 2 ), [Ag(XANTphos)(dicnq)]CF₃SO₃ ( 3 ), {[Ag(XANTphos)(dicnq)]NO₃}₂ ( 4 ), and [Ag(XANTphos)(dicnq)]ClO₄ · CH₂Cl₂ ( 5 ) {DPEphos = bis[2‐(diphenylphosphanyl)phenyl]ether, dicnq = 6,7‐dicyanodipyridoquinoxaline, XANTphos = 9,9‐dimethyl‐4,5‐bis(diphenylphosphanyl)xanthene} were characterized by X‐ray diffraction, IR, ¹H NMR, ³¹P NMR, fluorescence spectra, and terahertz time‐domain spectra (THz‐TDS). In the five complexes the Ag^I, which is coordinated by two kinds of chelating ligands, adopts four‐coordinate modes to generate mono‐nuclear structures. The C–H ··· π interactions lead to formation of a 1D infinite chain for complexes 2 and 3 . The crystal packing of complexes 1 and 5 reveal that they form 3D supermolecular network by several pairs of C–H ··· π interactions. The emissions of these complexes are attributed to ligands‐centered [π–π*] transition based on both of the P‐donor and N‐donor ligands.     

Three AgI,CuI and CdII coordination polymers based on the new asymmetrical ligand 2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole: syntheses,characterization and emission properties

The new asymmetrical organic ligand 2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole ( L , C₁₇H₁₃N₅O), containing pyridine and imidazole terminal groups, as well as potential oxdiazole coordination sites, was designed and synthesized. The coordination chemistry of L with soft Ag^I, Cu^I and Cd^II metal ions was investigated and three new coordination polymers (CPs), namely, catena‐poly[[silver(I)‐μ‐2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole] hexafluoridophosphate], {[Ag( L )]PF₆}_n, catena‐poly[[copper(I)‐di‐μ‐iodido‐copper(I)‐bis(μ‐2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole)] 1,4‐dioxane monosolvate], {[Cu₂I₂( L )₂]·C₄H₈O₂}_n, and catena‐poly[[[dinitratocopper(II)]‐bis(μ‐2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole)]–methanol–water (1/1/0.65)], {[Cd( L )₂(NO₃)₂]·2CH₄O·0.65H₂O}_n, were obtained. The experimental results show that ligand L coordinates easily with linear Ag^I, tetrahedral Cu^I and octahedral Cd^II metal atoms to form one‐dimensional polymeric structures. The intermediate oxadiazole ring does not participate in the coordination interactions with the metal ions. In all three CPs, weak π–π interactions between the nearly coplanar pyridine, oxadiazole and benzene rings play an important role in the packing of the polymeric chains.     

Syntheses and Crystal Structures of Copper(II) and Silver Complexes with 5‐Methyl‐1‐(4‐Methylphenyl)‐1,2,3‐Triazol‐4‐Carboxylic Acid

Two novel complexes [Cu L ₂(MeOH)] ( 1 )and [Ag₂ L (H L )₂(MeOH)] ( 2 ) ( L = 5‐methyl‐1‐(4‐methylphenyl)‐1,2,3‐triazol‐4‐carboxylic acid) were synthesized and characterized by elemental analysis, IR and X‐ray diffraction. Complex 1 is a mononuclear structure; the molecules were assembled into an infinite 2–D supramolecular by the C–H···O weak interactions. Complex 2 is a centrosymmetric dinuclear structure with bis(unidentate) carboxylato co‐ordination mode, and the molecules were assembled into 2–D layers by C–H···O and O–H···O weak interactions.     

Syntheses,Structures, Electrochemistry,and Electrocatalysis of Three Copper(II) Coordination Polymers constructed from 5‐[4‐(1H‐Imidazol‐1‐yl)phenyl]‐1H‐tetrazole

Three coordination polymers (CPs) based on the 5‐[4‐(1H‐imidazol‐1‐yl)phenyl]‐1H‐tetrazole ( HL ) ligand, namely, [Cu(μ₂‐ L )(μ₄‐pbda)(H₂O)] ( 1 ), [Cu₂(μ‐Hbtc)(H₂btc)(μ₃‐OH)(μ₄‐ HL )] ( 2 ) and [Cu₅(μ₃‐ L )(μ₄‐ L )(μ₃‐ip)(μ₃‐OH)(H₂O)₂] · 2H₂O ( 3 ) (H₂pbda = 1,4‐benzenedicarboxylic acid, H₃btc = 1,3,5‐benzenetricarboxylic acid, H₂ip = isophthalic acid) were hydrothermally synthesized and structurally characterized. Complex 1 represents “weave”‐type 2D layers consisting of wave‐like 1D chains and 1D straight chains, which are further connected by hydrogen bonds to form a 3D supramolecular structure. Complex 2 exhibits a uninodal (4)‐connected 2D layer with a point symbol of {4⁴ · 6²}, in which the L ligand can be described as μ₅‐bridging and the H₂btc^– ions display multiple kinds of coordination modes to connect Cu^II ions into 1D “H”‐type Cu‐H₂btc chains. In complex 3 , 2D Cu‐ L layers with two kinds of grids and 1D “stair”‐type Cu‐ip chains link each other to construct a 3D {4¹² · 6³} framework, which contains the pentanuclear subunits. Deprotonated degree and coordination modes of carboxylate ligands may consequentially influence the coordination patterns of main ligands and the final structures of complexes 1 – 3 . Furthermore, electrochemical behaviors and electrocatalytic activities of the title complexes were analyzed at room temperature, suggesting practical applications in areas of electrocatalytic reduction toward nitrite and hydrogen dioxide in aqueous solutions, respectively.     

Four Complexes with the Rigid Ligand 1,4‐Bis(1H‐imidazol‐4‐yl)benzene and Varied Carboxylate Ligands

Four metal‐organic coordination polymers [Co₂(L)₃(nipa)₂]·6H₂O ( 1 ), [Cd(L)(nipa)]·3H₂O ( 2 ), [Co(L) (Hoxba)₂] ( 3 ) and [Ni₂(L)₂(oxba)₂(H₂O)]·1.5L·3H₂O ( 4 ) were synthesized by reactions of the corresponding metal(II) salts with the rigid ligand 1,4‐bis(1H‐imidazol‐4‐yl)benzene (L) and different derivatives of 5‐nitroisophthalic acid (H₂nipa) and 4,4′‐oxybis(benzoic acid) (H₂oxba), respectively. The structures of the complexes were characterized by elemental analysis, FT‐IR spectroscopy and single‐crystal X‐ray diffraction. Complexes 1 and 3 have the same one‐dimensional (1D) chain while 2 is a 6‐connected twofold interpenetrating three‐dimensional (3D) network with α ‐Po 4¹²·6³ topology based on the binuclear Cd^II subunits. Compound 4 features a puckered two‐dimensional (2D) (4,4) network, and the large voids of the packing 2D nets have accommodated the uncoordinated L guest molecules. An abundant of N–H···O, O–H···O and C–H···O hydrogen bonding interactions exist in complexes 1–4 , which contributes to stabilize the crystal structure and extend the low‐dimensional entities into high‐dimensional frameworks. Lastly, the photoluminiscent properties of compounds 2 were also investigated.     

Copper(II) and Cadmium(II) Complexes Based on N,N‐Bis(3, 5‐dimethyl‐2‐hydroxybenzyl)‐N‐(2‐pyridylmethyl)amine Ligand: Syntheses,Structures, Magnetic,and Luminescent Properties

The reaction of the aryl‐oxide ligand H₂L [H₂L = N,N‐bis(3, 5‐dimethyl‐2‐hydroxybenzyl)‐N‐(2‐pyridylmethyl)amine] with CuSO₄ · 5H₂O, CuCl₂ · 2H₂O, CuBr₂, CdCl₂ · 2.5H₂O, and Cd(OAc)₂ · 2H₂O, respectively, under hydrothermal conditions gave the complexes [Cu(H₂L¹)₂] · SO₄ · 3CH₃OH ( 1 ), [Cu₂(H₂L²)₂Cl₄] ( 2 ), [Cu₂(H₂L²)₂Br₄] ( 3 ), [Cd₂(HL)₂Cl₂] ( 4 ), and [Cd₂(L)₂(CH₃COOH)₂] · H₂L ( 5 ), where H₂L¹ [H₂L¹ = 2, 4‐dimethyl‐6‐((pyridin‐2‐ylmethylamino)methyl)phenol] and H₂L² [H₂L² = 2‐(2, 4‐dimethyl‐6‐((pyridin‐2‐ylmethylamino)methyl)phenoxy)‐4, 6‐dimethylphenol] were derived from the solvothermal in situ metal/ligand reactions. These complexes were characterized by IR spectroscopy, elementary analysis, and X‐ray diffraction. A low‐temperature magnetic susceptibility measurement for the solid sample of 2 revealed antiferromagnetic interactions between two central copper(II) atoms. The emission property studies for complexes 4 and 5 indicated strong luminescence emission.     

Syntheses,Crystal Structures,and Properties of Three Copper(II) Complexes Constructed by 4‐(4,6‐Bis(1H‐pyrazol‐1‐yl)‐1,3,5‐triazin‐2‐yl)morpholine

Three copper(II) complexes of the polydentate N‐donor ligand [4‐(4,6‐bis(1H‐pyrazol‐1‐yl)‐1,3,5‐triazin‐2‐yl)morpholine] (L) with chlorides, nitrates, and perchlorates as anions, namely, [CuCl₂(L)] · 0.5(MeCN) ( 1 ), [Cu(NO₃)₂(H₂O)(L)] · (MeCN) ( 2 ), and [Cu(L)₂](ClO₄)₂ · (MeCN) ( 3 ) were synthesized and structurally characterized by IR, elemental analysis and X‐ray crystallographic analysis. In these complexes, the L ligand binds the copper(II) cation in the tridentate N₃ form. The coordination arrangement around the central copper(II) atom is distorted square‐pyramidal in 1 but it is distorted octahedral in 2 and 3 . The interesting noncovalent interactions such as hydrogen bonds, π–π stacking, and anion–π interactions present in the solid‐state structures are discussed. The crystal results reveal that the counteranions play important roles in determining the diverse structures of these complexes. Moreover, the PXRD, TG, DRS, and fluorescence properties of compounds 1 – 3 were investigated.     

Differing Coordination Modes of (O‐Alkyl)‐p‐Ethoxyphenyldithiophosphonato Ligands in Copper(I), Silver(I) and Gold(I) Triphenylphosphine Complexes

The three (O‐methyl)‐p‐ethoxyphenyldithiophosphonato triphenylphosphine complexes of copper, silver and gold, [(Ph₃P)_nM{S₂P(OMe)C₆H₄OEt‐p}] (M = Cu, n = 2; M = Ag, Au, n = 1) investigated structurally by X‐ray diffraction exhibit remarkable structural differences. The copper compound is a four‐coordinate chelate monomer with Cu–S 2.4417(6) and 2.5048(6) Å; P–Cu–S 104.24(2)–114.01(2)°; Cu–S–P 82.49(3)° and 80.85(2)°. The silver compound is a cyclic dimer with bridging dithiophosphonato ligands and three‐coordinate silver atoms [Ag–S 2.5371(5) and 2.6867(5) Å; P–Ag–S 122.88(2)° and 122.17(2)°; Ag–S–P 89.32(2)° and 103.56(2)°]. The gold compound is monomeric with linear dicoordinate gold [Au–S 2.3218(6) Å; P–Au–S 177.72(2)°, Au–S–P 100.97(3)°].     

Ligand‐forced dimerization of copper(I)–olefin complexes bearing a 1,3,4‐thiadiazole core

As an important class of heterocyclic compounds, 1,3,4‐thiadiazoles have a broad range of potential applications in medicine, agriculture and materials chemistry, and were found to be excellent precursors for the crystal engineering of organometallic materials. The coordinating behaviour of allyl derivatives of 1,3,4‐thiadiazoles with respect to transition metal ions has been little studied. Five new crystalline copper(I) π‐complexes have been obtained by means of an alternating current electrochemical technique and have been characterized by single‐crystal X‐ray diffraction and IR spectroscopy. The compounds are bis[μ‐5‐methyl‐N‐(prop‐2‐en‐1‐yl)‐1,3,4‐thiadiazol‐2‐amine]bis[nitratocopper(I)], [Cu₂(NO₃)₂(C₆H₉N₃S)₂], (1), bis[μ‐5‐methyl‐N‐(prop‐2‐en‐1‐yl)‐1,3,4‐thiadiazol‐2‐amine]bis[(tetrafluoroborato)copper(I)], [Cu₂(BF₄)₂(C₆H₉N₃S)₂], (2), μ‐aqua‐bis{μ‐5‐[(prop‐2‐en‐1‐yl)sulfanyl]‐1,3,4‐thiadiazol‐2‐amine}bis[nitratocopper(I)], [Cu₂(NO₃)₂(C₅H₇N₃S₂)₂(H₂O)], (3), μ‐aqua‐(hexafluorosilicato)bis{μ‐5‐[(prop‐2‐en‐1‐yl)sulfanyl]‐1,3,4‐thiadiazol‐2‐amine}dicopper(I)–acetonitrile–water (2/1/4), [Cu₂(SiF₆)(C₅H₇N₃S₂)₂(H₂O)]·0.5CH₃CN·2H₂O, (4), and μ‐benzenesulfonato‐bis{μ‐5‐[(prop‐2‐en‐1‐yl)sulfanyl]‐1,3,4‐thiadiazol‐2‐amine}dicopper(I) benzenesulfonate–methanol–water (1/1/1), [Cu₂(C₆H₅O₃S)(C₅H₇N₃S₂)₂](C₆H₅O₃S)·CH₃OH·H₂O, (5). The structure of the ligand 5‐methyl‐N‐(prop‐2‐en‐1‐yl)‐1,3,4‐thiadiazol‐2‐amine (Mepeta ), C₆H₉N₃S, was also structurally characterized. Both Mepeta and 5‐[(prop‐2‐en‐1‐yl)sulfanyl]‐1,3,4‐thiadiazol‐2‐amine (Pesta ) (denoted L ) reveal a strong tendency to form dimeric {Cu₂L ₂}²⁺ fragments, being attached to the metal atom in a chelating–bridging mode via two thiadiazole N atoms and an allylic C=C bond. Flexibility of the {Cu₂(Pesta )₂}²⁺ unit allows the Cu^I atom site to be split into two positions with different metal‐coordination environments, thus enabling the competitive participation of different molecules in bonding to the metal centre. The Pesta ligand in (4) allows the Cu^I atom to vary between water O‐atom and hexafluorosilicate F‐atom coordination, resulting in the rare case of a direct Cu^I…FSiF₅²⁻ interaction. Extensive three‐dimensional hydrogen‐bonding patterns are formed in the reported crystal structures. Complex (5) should be considered as the first known example of a Cu^I(C₆H₅SO₃) coordination compound. To determine the hydrogen‐bond interactions in the structures of (1) and (2), a Hirshfeld surface analysis has been performed.     

Luminescent Cu(I) and Ag(I) coordination polymers: Fast phosphorescence or thermally activated delayed fluorescence

By applying two donor-acceptor motif molecules, 5,10-di(pyridin-4-yl)-5,10-dihydrophenazine (L1) and 10,10'-di(pyridin-3-yl)-10H,10'H-9,9'-spiroacridine (L2), as ligands and CuI/AgCF₃CO₂ as metal salt, we synthesized three coordination polymers, namely, {Cu₄(L1)₂I₄} (CP1), {Cu(L2)I·CHCl₃} (CP2) and {Ag(L2)CO₂CF₃·CHCl₃} (CP3). X-ray crystallographic analysis revealed that three coordination polymers all feature one-dimensional (1D) linear chains which are consisting of molecular boxlike units. In comparison with low photoluminescence quantum yield (PLQY) of two ligands, three coordination polymers, CP1, CP2 and CP3, present more intense photoluminescence with PLQY of 15%, 46% and 34% at room temperature respectively. The PL emission of CP1 and CP2 at room temperature could be attributed to the fast phosphorescence with lifetime both around 5 μs due to effective intersystem crossing (ISC). Whilst, it is worth noting that CP3 exhibit thermally activated delayed fluorescence (TADF) emission at room temperature.     

Anion‐directed Silver(I) Coordination Assemblies Based on 1‐(2‐Pyridyl)‐2‐(4‐pyridyl)‐1,2,4‐triazolewith Diverse Supramolecular Networks and Dichromate Removal Capabilities

A series of silver(I) supramolecular complexes, namely, {[Ag(L²⁴)](NO₃)}_n ( 1 ), [Ag₂(L²⁴)(NO₂)₂]_n ( 2 ), and {[Ag_1.25(L²⁴)(DMF)](PF₆)_1.25}_n ( 3 ) were prepared by the reactions of 1‐(2‐pyridyl)‐2‐(4‐pyridyl)‐1,2,4‐triazole (L²⁴) and silver(I) salts with different anions (AgNO₃, AgNO₂, AgPF₆). Single‐crystal X‐ray diffraction indicates that 1 – 3 display diverse supramolecular networks. The structure of dinuclear complex 1 is composed of a six‐membered Ag₂N₄ ring with the Ag ··· Ag distance of 4.4137(3) Å. In complex 2 , the adjacent Ag^I centers are interlinked by L²⁴ ligands into a 1D chain, the adjacent of which are further extended by the bridged nitrites to construct a 2D coordination architecture. Complex 3 shows a 3D (3,4)‐connected framework, which is generated by the linkage of L²⁴ ligands. All complexes were characterized by IR spectra, elemental analysis, and powder X‐ray diffraction. Notably, a structural comparison of the complexes demonstrates that their structures are predominated by the nature of anions. Additionally, 1 and 2 show efficient dichromate (Cr₂O₇^2–) capture in water system, which can be ascribed to the anion‐exchange.     

Copper(II) Complexes with N‐(9‐anthracenyl)‐N′‐(3‐pyridyl)urea (L) and a Derivative of L: Synthesis,Structure, and Fluorescent Properties

Three copper(II) complexes, [Cu₂(OAc)₄L₂] · 2CH₃OH ( 1 ), [CuBr₂L′₂(CH₃OH)] · CH₃OH ( 2a ), and [CuBr₂L′₂(DMSO)] · 0.5CH₃OH ( 2b ) {L = N‐(9‐anthracenyl)‐N′‐(3‐pyridyl)urea and L′ = N‐[10‐(10‐methoxy‐anthronyl)]‐N′‐(3‐pyridyl)urea} have been synthesized by the reaction of L with the corresponding copper(II) salts. Complex 1 shows a dinuclear structure with a conventional “paddlewheel” motif, in which four acetate units bridge the two Cu^II ions. In complexes 2a and 2b , the anthracenyl ligand L has been converted to an anthronyl derivative L′, and the central metal ion exhibits a distorted square pyramidal arrangement, with two pyridyl nitrogen atoms and two bromide ions defining the basal plane and the apical position is occupied by a solvent molecule (CH₃OH in 2a and DMSO in 2b ).     

The heterometallic cadmium–silver complex cis‐bis[dicyanidoargentato(I)‐κN]bis(5,5′‐dimethyl‐2,2′‐bipyridyl‐κ2N,N′)cadmium(II) monohydrate

In the title complex, [Ag₂Cd(CN)₄(C₁₂H₁₂N₂)₂]·H₂O or cis‐[Cd{Ag(CN)₂}₂(5,5′‐dmbpy)₂]·H₂O, where 5,5′‐dmbpy is 5,5′‐dimethyl‐2,2′‐bipyridyl, the asymmetric unit consists of a discrete neutral [Cd{Ag(CN)₂}₂(5,5′‐dmbpy)₂] unit and a solvent water molecule. The Cd^II cation is coordinated by two bidentate chelate 5,5′‐dmbpy ligands and two monodentate [Ag^I(CN)₂]⁻ anions, which are in a cis arrangement around the Cd^II cation, leading to an octahedral CdN₆ geometry. The overall structure is stabilized by a combination of intermolecular hydrogen bonding, and Ag^I...Ag^I and π–π interactions, forming a three‐dimensional supramolecular network.     

Synthesis and characterization of three dinuclear copper(I) complexes of 1,2‐bis(diphenylphosphino)‐1,2‐dicarba‐closo‐dodecaborane

Three dinuclear copper(I) complexes, [Cu₂(µ‐Cl)₂(1,2‐(PPh₂)₂‐1,2‐C₂B₁₀H₁₀)₂]·2CH₂Cl₂ ( 1 ), [Cu₂(µ‐Br)₂(1,2‐(PPh₂)₂‐1,2‐C₂B₁₀H₁₀)₂]·2THF ( 2 ) and {Cu₂(µ‐I)₂[1,2‐(PPh₂)₂‐1,2‐C₂B₁₀H₁₀]₂} ( 3 ) have been synthesized by the reactions of CuX (X = Cl, Br and I) with the closo ligand 1,2‐(PPh₂)₂‐1,2‐C₂B₁₀H₁₀. All these complexes were characterized by elemental analysis, FT‐IR, ¹H and ¹³C NMR spectroscopy and X‐ray structure determination. Single crystal X‐ray structure determinations show that every complex contained di‐µ‐X‐bridged structure involving a crossed parallelogram plane formed by two Cu atoms and two X atoms (X = Cl, Br, I). The geometry at the Cu atom was a distorted tetrahedron, in which two positions were occupied by two P atoms of the PPh₂ groups connected to the two C atoms of carborane (Cc), and the other two resulted from two X atoms which bridged the other Cu atom at the same time. To the best of our knowledge, this is the first example of copper(I) complexes with 1,2‐diphenylphosphino‐1,2‐dicarba‐closo‐dodecaborane as ligand characterized by X‐ray diffraction. The catalytic property of the complex 3 for the amination of iodobenzene with aniline was also investigated. Copyright © 2005 John Wiley & Sons, Ltd.     

Thallium(I), Silver(I), and Mixed Thallium(I)/Copper(I) Clusters with Bridging {Me2Si(N‐C6H4‐2‐SPh)2}2– Ligands

The S‐functionalized aminosilane Me₂Si(NH‐C₆H₄‐2‐SPh)₂ (H₂L) ( 1 ) was prepared from dichlorodimethylsilane and lithiated 2‐(phenylthio)aniline. Treatment of compound 1 with two equivalents of n‐butyllithium led to the dilithium derivative Li₂L, which was used in subsequent reactions with MCl (M = Tl, Cu, Ag) to prepare the complexes [Tl₂L] ( 2 ), [Cu₂Tl₂L₂] · 2THF ( 3a ), [Cu₂Tl₂L₂(THF)₂] ( 3b ), and [Ag₄L₂(THT)₂] ( 4 ) (THT = tetrahydrothiophene). Compound 2 consists of two thallium atoms, which are connected by a L^2– ligand to give a puckered Tl₂N₂ ring with Tl–N distances of 255(1)–268(1) pm. Compounds 3a and 3b are heterobimetallic complexes, which are based on [Cu₂L₂]^2– cores featuring a Cu₂N₄Si₂ ring with linearly coordinated copper atoms [Cu–N: 190.7(3)–192.5(3) pm] and two peripherally attached Tl atoms [Tl–N: 272.7(3)–281.9(3) pm]. The molecular structure of the tetranuclear silver(I) complex 4 is closely related to the structure of compounds 3a and 3b by replacement of the Cu and Tl atoms with Ag atoms. The Ag–N distances are 217.5(3)–245.7(3) pm.     

Preparation,Structure, Spectral,and Magnetic Properties of Copper(II) Halogenonicotinates: Crystal and Molecular Structure of Tetrakis(μ‐2‐chloronicotinato‐O,O′)‐diaquadicopper(II)

The characterization of the complexes [Cu₂(2‐Clnic)₄(H₂O)₂] ( 1 ), [Cu(2,6‐Cl₂nic)₂(H₂O)₂] ( 2 ) and [Cu(5‐Brnic)₂(H₂O)₂]_n ( 3 ) (where 2‐Clnic = 2‐chloronicotinate, 2,6‐Cl₂nic = 2,6‐dichloronicotinate or 5‐Brnic = 5‐bromonicotinate) was based on elemental analysis, IR, electronic and EPR spectra, and magnetic susceptibility. Complex 1 was also studied by X‐ray analysis at 298 1a and 80 K 1b . The complex 1 contains a dinuclear Cu‐acetate molecular structure in which the carboxyl groups of the 2‐chloronicotinate ligands act as bridges and water molecules are at apical positions. The stereochemistry about Cu atom at both temperatures is typical for square pyramidal geometry with CuO₄O chromophore. The Cu‐Cu distance is 2.6513(8) and 2.6382(6) Å for 1a and 1b , respectively. The Cu atoms are displaced by 0.2069(9) and 0.1973(7) Å, respectively, from the plane containing four oxygen atoms bonded to the Cu atom toward the apical water molecules. Strong and weak hydrogen bonds as well as C–Cl···π interactions in the crystal structure are discussed as well. Both complexes, monomeric [Cu(2,6‐Cl₂nic)₂(H₂O)₂] ( 2 ) and polymeric [Cu(5‐Brnic)₂(H₂O)₂]_n ( 3 ), possess octahedral copper(II) stereochemistry with differing tetragonal distortions.     

Synthesis,Characterization, and Luminescent Properties of Silver(I) Complexes based on Diphosphine Ligands and 2,9‐Dimethyl‐1,10‐phenanthroline

Five mono‐nuclear silver(I) complexes with the ligand 2,9‐dimethyl‐1,10‐phenanthroline, namely [Ag(DPEphos)(dmp)]BF₄ ( 1 ), [Ag(DPEphos)(dmp)]CF₃SO₃ ( 2 ), [Ag(DPEphos)(dmp)]ClO₄ ( 3 ), [Ag(DPEphos)(dmp)]NO₃ ( 4 ), and [Ag(dppb)(dmp)]NO₃ · CH₃OH ( 5 ) {DPEphos = bis[2‐(diphenylphosphanyl)phenyl]ether, dppb = 1,2‐bis(diphenylphosphanyl)benzene, dmp = 2,9‐dimethyl‐1,10‐phenanthroline} were characterized by X‐ray diffraction, IR, ¹H NMR, ³¹P NMR and fluorescence spectroscopy. Their terahertz (THz) time‐domain spectra were also studied. In these complexes the silver(I), which is coordinated by two kinds of chelating ligands, adopts four‐coordinate modes to generate mono‐nuclear structures. In complexes 1 , 3 – 5 , offset π ··· π weak interactions exist between the neighboring benzene rings. In the ³¹P NMR spectra, there exist splitting signals (dd), which can be attributed to the coupling of the ^107,109Ag–³¹P. All the emission peaks of these complexes are attributed to ligand‐centered excited states.