Phenylcyanamide Ligands Research Articles

The discovery of half-sandwich iridium complexes containing lidocaine and (pyren-1-yl)ethynyl derivatives of phenylcyanamide ligands for photodynamic therapy.

The successful design, synthesis, characterization, photophysical properties and anticancer mechanistic studies of a series of half-sandwich cyclopentadienyl iridium(iii) complexes of the type [Cp*IrIII(LC)(L1)](PF6), 1, and [Cp*IrIII(LC)(L2)](PF6), 2, in which Cp* = pentamethylcyclopentadienyl, L1 = 4-(pyren-10-yl)ethynyl-phenylcyanamide, L2 = 4'-(pyren-10-yl)ethynyl-4-cyanamidobiphenyl, and LC = lidocaine, are reported for their application as photodynamic therapy (PDT) agents. The DNA binding, DNA photocleavage, cellular uptake, and apoptosis of the complexes have also been studied.

A new Ag-nanoparticle with 4-nitro phenylcyanamide ligand: synthesis characterization and application to the detection of dibucaine, naphazoline, dopamine, and acetaminophen

In this research, Ag(I) nanoparticle with 4-nitro phenylcyanamide ligand, [AgL] n , where L = 4-nitro phenylcyanamide (4-NO2pcyd), was synthesized successfully. FT-IR, 1H-NMR, TGA, and UV–Vis studies were done for the structural and thermal characterization of the Ag(I) nanoparticle. The spherical morphology of silver nanoparticles was confirmed from SEM image. The transmission electron microscopy image showed that the particle size dimensions of silver nanoparticles were about 1.5–5 nm. Furthermore, Ag(I) nanoparticle was immobilized on the surface of a glassy carbon electrode (GCE), and the electroactivity behavior was investigated by cyclic voltammetry and differential pulse voltammetry (DPV). The obtained [AgL] n -modified GCE showed high catalytic activity for the oxidation of dibucaine and naphazoline. The peak current of differential pulse voltammograms of dibucaine and naphazoline increased linearly with their concentration in the ranges of 2.17–5.74 µM naphazoline and 18.5–72.2 µM dibucaine. The detection limits for dibucaine and naphazoline were 0.002 and 0.009 µM, respectively. In addition, the obtained [AgL] n -modified GCE was investigated for the simultaneous determination of dopamine (DA) and acetaminophen (AP). In DPV technique, both DA and AP give sensitive oxidation peaks at 130 and 312 mV, respectively. Under the optimized experimental conditions, DA and AP give linear response over the range of 5–200 µmol L−1 (r = 0.996) and 5–300 µmol L−1 (r = 0.994), respectively. The lower detection limits were found to be 0.7 for DA and 0.5 µmol L−1 for AP. The investigated method showed good stability, reproducibility [1.4 % (DA) and 2.5 % (AP)], and repeatability (1.8 %).

Syntheses, studies and crystal structure of new coordination polymers of mercury (II) with phenylcyanamide derivative ligands

A series of compounds mercury (II), [Hg(CH2COCH3)L]n where L=anion of 4-NO2pcyd (4-nitro phenylcyanamide) (1), 4-Clpcyd (4-chloro phenylcyanamide) (2), 4-Brpcyd (4-bromo phenylcyanamide) (3) were synthesized from acetone and characterized by elemental analysis, IR, 1H NMR, 13C NMR and electronic absorption spectroscopies. Single crystal X ray analysis of 1 reveals coordination of phenylcyanamide ligand to Hg (II) unexpectedly occurred through amine nitrogen alone which is rare. Also the anion of acetone was coordinated to mercury by the carbon atom as well as oxygen atom from (CO) of another acetone anion. A theoretical study at DFT (B3LYP) level showed that the experimentally determined structure of the complex 1 is about 6.49 and 8.31kcal/mol, respectively in the gas phase and solvent more stable than its other bonding modes. In addition, this phenomenon was supported by NBO interaction energies and the much orbital contribution in the HOMO of ligand to interact with Hg (II) that all of these observations were raised from the presence of nitro group as electron withdrawing group. By using TD-DFT method, electronic absorption spectra of the compound 1 have been predicted and a good agreement with the TD-DFT method and the experimental one is determined. Biological studies show the antibacterial activity of the complex 1 against Gram-positive and Gram-negative bacterial strains.

Phenylcyanamide Ligand Control of Photo-Induced Linkage Isomerism

The photo- and electrochemically induced linkage isomerism of six new complexes [Ru(bpy)2(L)(dmso-S)](+), where dmso is dimethylsulfoxide, bpy is 2,2'-bipyridine, and L(-) is pentachloro-, 2,3,5,6-tetrachloro-, 2,4,5-trichloro-, 2,4-dichloro-, 4-chloro-, and unsubstituted phenylcyanamide anion, were investigated. The quantum yields of linkage isomerism forming the metastable [Ru(bpy)2(L)(dmso-O)](+) complexes are shown to decrease with increasing donor properties of the phenylcyanamide ligand, and it is suggested that the donor properties of the cyanamide ligand stabilize the [Ru(bpy)2(L)(dmso-S)](+) complexes in the (3)MLCT excited state. The cyclic voltammetry of these complexes showed two oxidation processes: a phenylcyanamide L(0/-) couple (an assignment supported by density functional theory (DFT) calculations) and a Ru(III/II) couple at more positive potential. Upon oxidation to Ru(III), the complexes rearranged to form Ru-O linkage isomers, and the scan rate dependent voltammograms permitted estimates of the rates of linkage isomerism.

Lanthanum(III) complexes with phenylcyanamide ligands: Synthesis and crystal structure

Several novel mixed ligand lanthanum complexes with 1,10-phenantroline and phenylcyanamide derivatives with the formula of [La(phen)3Cl3·OH2] (1) and [La(phen)3L3] (phen=1,10-phenantroline; L=2-clorophenylcyanamide (2), 2,5-dichlorophenylcyanamide (3), 2,4-dichlorophenycyanamide (4) and 2,4,5-trichorophenycyanamide (5)) are successfully synthesized in aqueous solution. The complexes are characterized by spectroscopic analysis such as infrared, 1H NMR, UV–Vis spectroscopy as well as elemental analysis. The molecular structure of 3 is determined by single-crystal X-ray diffraction method. Three 2,5-Cl2pcyd and three phenanthroline ligands are coordinated to the central La atom in monodentate and bidentate manner, respectively.

EPR and 1H NMR spectroscopy and DFT study of pentaammineruthenium(III)phenylcyanamide complexes

The EPR and 1H NMR spectroscopy of seven [Ru(NH3)5L]2+ complexes, where L=3,5-dimethoxyphenylcyanamide (MeO2pcyd), 3,4,5-trimethoxyphenylcyanamide (MeO3pcyd), 4-nitrophenylcyanamide (NO2pcyd), 2,3-dichlorophenylcyanamide (Cl2pcyd), 2,4,6-trichlorophenylcyanamide (Cl3pcyd), 2,3,5,6-tetrachlorophenylcyanamide (Cl4pcyd) and pentachlorophenylcyanamide (Cl5pcyd), was performed. EPR spectra of the complexes showed an axial signal with g|| and g⊥ at high and low field, respectively. The g|| axis is suggested to lie along the Ru–cyanamide bond. Gas-phase DFT calculations of [Ru(NH3)5 phenylcyanamide]2+ showed spin density localized mostly on the phenylcyanamide ligand, in disagreement with EPR data. DFT/polarizable continuum model (PCM, water solvation) calculations shifted spin density towards ruthenium so that spin density was shared between ruthenium and phenylcyanamide ligand. Proton contact shifts were determined from NMR and EPR data and were used to estimate spin density distributions on phenyl ring carbons. The results showed that the DFT/PCM calculation overestimated spin density on phenyl ring carbons by approximately one order of magnitude. Donor–acceptor interactions between the solute and solvent that are not fully accounted for in the DFT/PCM method are suggested to stabilize the Ru(III) oxidation state.

Synthesis, Electrochemical Properties and Spectroscopic Studies of Mono and Dinuclear Zn(II) Polypyridyl Complexes with Phenylcyanamide Ligands

Several novel mononuclear Zn(II) complexes, [Zn(bpy)L2], where bpy=2,2’-bipyridine and L=monoanions of phenylcyanamide (pcyd), 4-methylphenylcyanamide (4-Mepcyd), 3,5-dimethylphenylcyanamide(3,5-Me2pcyd),4-methoxyphenylcyanamide(4-MeOpcyd), 3,5-dimeth-oxyphenylcyanamide (3,5-MeO2pcyd), 3-chlorophenylcyanamide (3-Clpcyd), 2,3-dichlorophenyl-cyanamide (2,3-Cl2pcyd), 4-bromophenylcyanamide (4-Brpcyd), 1-naphthylcyanamide (1-ncyd), azophenylcyanamide (apcyd) and a dinuclear Zn(II) complex, [{Zn(terpy)}2(μ-adicyd)](PF6)2, where terpy = 2,2´:6´,2´´-terpyridine and adicyd = azodi (phenylcyanamide) dianion have been synthesized and characterized by elemental analysis, UV-vis, IR, 1H-NMR spectroscopic techniques and cyclicvoltammetry.The presence of only one sharp and intense absorption band for υ(N=C=N) around 2100-2180 cm-1 for all the monomer complexes provide evidence that both cyanamide legend are equivalent in the solid state and coordinated end-on by nitride nitrogen to Zn(II). This is also indicated by 1H-NMR spectra of the complexes. UV-vis spectra show one MLCT band that are associated with Zn(II)-pyridyl chromophores(t2g6 →π*). Blue shift of this band with increasing the polarity of solvent from CH3OH to DMSO is the reason for this assignment. The Zn(II) ion is redox innocent therefore, two irreversible oxidation peaks at positive potential and one reduction couple at the negative potential are assigned to sequential oxidation of two phenylcyanamide ligands and reduction of bipyridine, respectively.

Synthesis and characterization of monomer and dimer complexes of porphyrin iron(III) with bridging phenylcyanamide ligands

Several new mono and dinuclear complexes of [(P)Fe III(L)], in which P is the dianion of tetraphenylporphyrin(TPP) and tetramesitylporphyrin(TMP) and L is the monoanion of 4-azo(phenylcyanamido)benzene (apc) ( 1) and ( 2) or dianion 1,4-di cyanamidobenzene (dicyd) ( 3), ( 4), ( 7), ( 8) and 4,4′-azo-diphenylcyanamide (adpc) ( 5), ( 6), ( 9), ( 10) have been prepared by the reaction of [(P)Fe IIICl] with appropriate thallium salts of phenylcyanamide derivatives. Each of the complexes has been characterized by FT-IR, UV–Vis, 1H NMR, MALDI-TOF and EPR spectroscopic data. In non-coordinating solvents (such as toluene or chloroform) these complexes exhibit 1H NMR spectra that are characteristic of high-spin (S = 5/2) species. The cyanamide group (NCN) of the bridging ligand is coordinated to Fe(III) ions through the nitrile-nitrogen. The iron(III) phenylcyanamide complexes are not reactive toward dioxygen, they convert into [TPPFe IIICl] when treated with HCl. EPR and NMR have shown that in dinuclear complexes weak magnetic interactions take place between two iron(III) paramagnetic centers.

Synthesis and structural determination of new octaethylporphyrin iron(III) complexes containing cyanamide derivatives as axial ligand

The reactions of heme, [OEPFeCl] where OEP is the dianion of octaethylporphyrin, with phenylcyanamide (pcyd) ligands have been studied. Four new porphyrin complexes, [OEPFe(L)] (L = pcyd ( 2), 2-Clpcyd ( 3), 2-Mepcyd ( 4), 2,4-Me 2pcyd ( 5)), have been isolated and characterized by spectroscopic methods. 1H NMR spectroscopy reveals that the species [OEPFe(L)] are paramagnetic and iron is five-coordinate. The structure of [OEPFe(pcyd)] ( 2) has been determined by X-ray diffraction analysis. The four Fe–N, bond distances have average values of 2.062 Å. The average displacement of the iron(III) atom from the mean porphinato core is 0.45 Å. Electrochemical of [OEPFe(L)] (L = pcyd ( 2), 2-Clpcyd ( 3), 2-Mepcyd ( 4), 2,4-Me 2pcyd ( 5)) have been studied by cyclic voltammetry.

Synthesis and characterization of tetraphenylporphyrin iron(III) complexes with substituted phenylcyanamide ligands

Several five coordinate complexes of [(TPP)Fe III(L)] in which TPP is the dianion of tetraphenylporphyrin and L is the monoanion of phenylcyanamide (pcyd) ( 1), 2,5-dichlorophenylcyanamide (2,5-Cl 2pcyd) ( 2), 2,6-dichlorophenylcyanamide (2,6-Cl 2pcyd) ( 3), and 2,3,4,6-tetrachlorophenylcyanamide (2,3,4,6-Cl 4pcyd) ( 4) have been prepared by the reaction of [(TPP)Fe IIICl] with appropriate thallium salt of phenylcyanamide. Each of the complexes has been characterized by IR, UV–Vis and 1H NMR spectroscopic data. Dark red-brown needles of [(TPP)Fe III(2,6-Cl 2pcyd)] (C 51H 31Cl 2FeN 6 · CHCl 3) crystallize in the triclinic system. The crystal structure of Fe(III) compound shows a slight distortion from square pyramidal coordination with the 2,6-dichlorophenylcyanamide anion in the axial position through nitrile nitrogen atom. Iron atom is 0.47(1) Å out of plane of the porphyrin toward phenylcyanamide ligand. In non-coordinating solvents, such as benzene or chloroform, these complexes exhibit 1H NMR spectra that are characteristic of high-spin ( S = 5/2) species. The X-ray crystal structure parameters are also consistent with high-spin iron(III) complexes. The iron(III) phenylcyanamide complexes are not reactive toward molecular oxygen; however, these complexes react with HCl and produce TPPFe IIICl.

Synthesis and characterization of tetraphenylporphyrin manganese(III) complexes of phenylcyanamide ligands

Several complexes of TPPMn–L, where TPP is the dianion of tetraphenylporphyrin and L is monoanion of 4-methylphenylcyanamide (4-Mepcyd) ( 1), 2,4-dimethylphenylcyanamide (2,4-Me 2pcyd) ( 2), 3,5-dimethylphenylcyanamide (3,5-Me 2pcyd) ( 3), 4-methoxyphenylcyanamide (4-MeOpcyd) ( 4), phenylcyanamide (pcyd) ( 5), 2-chlorophenylcyanamide (2-Clpcyd) ( 6), 2,5-dichlorophenylcyanamide (2,5-Cl 2pcyd) ( 7), 2,6-dichlorophenylcyanamide (2,6-Cl 2pcyd) ( 8), 4-bromophenylcyanamide (4-Brpcyd) ( 9), and 2,3,4,5-tetrachlorophenylcyanamide (2,3,4,5-Cl 4pcyd) ( 10), have been prepared from the reaction of TPPMnCl and thallium salt of related phenylcyanamide. Each of the complexes has been characterized by IR, UV–Vis and 1H NMR spectroscopies. 4-Methylphenylcyanamidotetraphenylporphyrin manganese(III) crystallized with one molecule of solvent CHCl 3 in the triclinic crystal system and space group P 1 ¯ with the following unit cell parameters of: a = 11.596(6) Å; b = 11.768(9) Å; c = 17.81(2) Å; and α, β, γ are 88.91(9)°, 88.16(7)°, 67.90(5)°, respectively; V = 2251(3) Å 3; Z = 2. A total of 4234 reflections with I > 2 σ( I) were used to refine the structure to R = 0.0680 and R w = 0.2297. The Mn(III) shows slightly distorted square pyramidal coordination with the 4-methylphenylcyanamide in the axial position, coordinated from nitrile nitrogen. The reduction of each of the TPPMn–L complexes was also examined in dichloromethane and spectroelectrochemical behavior of ( 1) was investigated and compared to TPPMnCl.

Structure and spectroscopic studies of cis-bis(bipyridine) ruthenium(II) complexes of phenylcyanamide ligands

New ruthenium(II) complexes with cyanamide ligands, cis-[Ru(bpy) 2(Ipcyd) 2] ( 1) and [Ru(bpy) 2(OHpcyd) 2] ( 2) (bpy = 2,2′-bipyridine, Ipcyd = 4-iodophenylcyanamide anion, OHpcyd = 4-(3-hydroxy-3-methylbut-1-ynil)phenylcyanamide), have been prepared and characterized by UV–Vis, IR and 1H NMR spectroscopies as well as electrochemical technique (CV). The complex cis-[Ru(bpy) 2(Ipcyd) 2] ( 1) crystallized with empirical formula of C 34H 24I 2N 8Ru in a monoclinic crystal system and space group of P2 1/c with a = 11.769(7) Å, b = 24.188(12) Å, c = 11.623(2) Å, β = 91.63(3)°, V = 3308(3) Å 3 and Z = 4.

New examples of the unusual X-phenylcyanamido bridging ligands. Crystal structure and magnetic properties of Mn II derivatives

Several new Mn II compounds with X-phenylcyanamido (Xpcyd) and 1,10-phenantroline (phen) ligands of formula [Mn(3-Clpcyd)(H 2O)(phen) 2](NO 3) · H 2O ( 1), [{Mn(3-Fpcyd)(MeOH)(phen)} 2(μ-3-Fpcyd) 2] ( 2), [{Mn(3-Fpcyd)(EtOH)(phen)} 2(μ-3-Fpcyd) 2] ( 3), [{Mn(3-Clpcyd)(MeOH)(phen)} 2(μ-3-Clpcyd) 2] ( 4) and [{Mn(4-Clpcyd)(EtOH)(phen)} 2(μ-4-Clpcyd) 2] ( 5) have been synthesised and characterised. Mononuclear compound 1 crystallises in the monoclinic system, P2 1/ c space group, dinuclear compounds 2– 5 crystallise in the monoclinic system, C2/ c space group 2, triclinic system, P 1 ̄ space group 3– 4 and in the monoclinic system, P2 1/ a space group 5. These compounds contain the unusual end-to-end R-cyanamide bridge and give supramolecular one-dimensional networks by means of H-bonds involving the N-amide atoms of the phenylcyanamide ligands. Susceptibility measurements on compounds 2– 5 reveal moderate AF coupling in all cases. Coupling constants related to the phenylcyanamido bridges are compared with the superexchange model recently proposed for ligands of this kind.

Structure and spectroscopic studies of cis-bis(bipyridine) cobalt(III) complexes of phenylcyanamide ligands

Several new cobalt complexes, cis-[(bpy) 2Co(L) 2]PF 6, where bpy=2,2′-bipyridine and L=monoanion of phenylcyanamide (pcyd), 2-chlorophenylcyanamide(2-Clpcyd), 2,5-dichlorophenylcyanamide(2,5-Cl 2pcyd), 2-methylphenylcyanamide(2-Mepcyd) and 2,4-dimethylphenylcyanamide(2,4-Me 2pcyd) have been prepared and characterized by UV–Vis, IR and 1H NMR spectroscopies. The complex of cis-[(bpy) 2Co(2-Clpcyd) 2]PF 6 crystallized with one third of a molecule of acetonitrile with empirical formula of C 34.67H 25N 8.33F 6Cl 2PCo, in a triclinic crystal system and space group of P 1 ̄ with a=10.937(1) Å, b=12.716(1) Å, c=13.452(1) Å, β=91.019(4)°, V=1789.3(3) Å 3, and Z=2. The structure was refined by using 5385 Mo Kα reflections with I>3 σ( I) and R factor of 0.065. These Co-complexes possess low-energy ligand to metal charge-transfer bands associate with Co(III)NCN chromophore. Comparison between the properties of cis-[Ru(bpy) 2(L) 2]PF 6 and cis-[Co(bpy) 2 (L) 2]PF 6 complexes shows the same behavior in the covalency of the MNCN π-bond.

Unusual properties of ruthenium(II) diphenylcyanamide complexes: chemistry and application as sensitizers of nanocrystalline TiO2

In this study, a series of ruthenium(II) polypyridyl complexes of the general formula Na4[RuII(dcbpy)2X2] (dcbpy is 2,2′-bipyridine-4,4′-dicarboxylate and X is a substituted phenylcyanamide anion) are investigated. When introduced into the ruthenium co-ordination sphere, the phenylcyanamide ligand showed linkage isomerism and was co-ordinated via the nitrile- or amide nitrogen, as shown by 1H NMR, 13C NMR spectroscopy and use of a 13C-labeled ligand. The title compounds exhibited unusually high first pKa values between 5 and 6, determined via spectrophotometric titrations. The first protonation occurred at the phenylcyanamide ligand, rendering the energy of the lowest energy 1MLCT absorption strongly pH-dependent. In photovoltaic devices, overall efficiencies were in the range of 3–4%, due to photon-to-current conversion efficiencies of 50–60% at 520 nm. The long-term stability of a representative complex under irradiation was investigated in solution and in a solar cell device.

(Terpyridine)palladium(II) complexes of phenylcyanamide ligands

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXT(Terpyridine)palladium(II) complexes of phenylcyanamide ligandsWeigang Zhang, Corinne Bensimon, and Robert J. CrutchleyCite this: Inorg. Chem. 1993, 32, 25, 5808–5812Publication Date (Print):December 1, 1993Publication History Published online1 May 2002Published inissue 1 December 1993https://doi.org/10.1021/ic00077a026RIGHTS & PERMISSIONSArticle Views446Altmetric-Citations33LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (511 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

The Dependence of Ligand to Metal Charge Transfer Oscillator Strength on the Nature of the Ruthenium (III)-Cyanamide Bond: Outersphere Perturbations

Abstract The extent of electronic coupling between donor and acceptor wave-functions can play a dominant role in determining the rate of electron transfer. This is particularly true for biological electron transfer systems in which the redox sites are far apart or linked by a bridging ligand. In this study, we have investigated the extent to which electronic coupling between Ru(III) and an an — ionic phenylcyanamide ligand as measured by the b1* ← b1 LMCT oscillator strength is affected by the nature of the outer coordination sphere. The LMCT oscillator strength was found to decrease with increasing solvent donor number. We suggest that the trend in oscillator strength can largely be rationalized in terms of the magnitude of the π overlap between Ru(III) and cyanamide anion group. When the cyanamide anion group is incorporated into the bridging ligand of a Ru(III, II) mixed—valence complex, the oscillator strength of the resulting LMCT band will be a probe of the extent to which the acceptor wavefunction ...

Synthetic, spectroscopic, and X-ray crystallographic studies on phenylcyanamidocopper(II) complexes. The characterization of three different co-ordination modes for phenylcyanamide anions

Phenylcyanamidocopper(II) complexes of the type [{CuL(L′)2}2][L = 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen), L′= a phenylcyanamide ion, XC6H4NCN–], [CuL2(L′)2](L = pyridine or piperidine), and [{CuL(L′)(CH3CO2)}2](L = bipy or phen) have been prepared from the reaction of the neutral phenylcyanamides with copper(II) acetate monohydrate in the presence of the appropriate N-donor co-ligand. They have been characterized by magnetic, i.r., and electronic spectral techniques and the crystal and molecular structures of [{Cu(bipy)(PhNCN)2}2] and [{Cu(phen)(3-ClC6H4NCN)(CH3CO2)}2]·2H2O determined by single-crystal X-ray diffraction techniques. Crystals of [{Cu(bipy)(PhNCN)2}2] are monoclinic, space group P21/c, with a= 9.625(3), b= 20.945(5), c= 9.956(3)A, β= 97.10(2)°, and Z= 2. The complex consists of discrete centrosymmetric dimers. The copper atom of each monomeric unit is co-ordinated equatorially to two bipy nitrogens [Cu–N 2.012(5) and 2.052(5)A] and to the cyano-nitrogens of two phenylcyanamide ligands [Cu–N 1.938(5) and 1.942(6)A]. The distorted square-pyramidal geometry is completed by a longer axial bond [2.355(6)A] to the amido nitrogen of one of the phenylcyanamide ligands of the other half of the dimer. Crystals of [{Cu(phen)(3-ClC6H4NCN)(CH3CO2)}2]·2H2O are triclinic, space group P, with a= 8.171 (5), b= 10.060(6), c= 13.377(7)A, α= 74.33(4), β= 84.79(5), γ= 72.24(4)°, and Z= 1. The complex consists of discrete centrosymmetric dimers, dimerization being achieved by the cyano nitrogen of the 3-chloro-phenylcyanamide ligand asymmetrically bridging two copper atoms, which have an approximate square-pyramidal co-ordination geometry. The cyano nitrogen [Cu–N 1.950(6)A], two phen nitrogens, and an acetate oxygen make an ‘ON3’ basal plane. A longer apical bond to the cyano nitrogen of the cyanamide ligand of the other half of the dimer [Cu–N 2.454(6)A] completes the co-ordination. The identification of three different co-ordination modes for the anionic phenyl-cyanamide ligands establishes their ambidentate nature.

Coordination chemistry of neutral phenylcyanamide ligands bound to pentaammineruthenium(II)

A general synthesis of pentaammineruthenium(II) complexes of phenylcyanamide ligands is presented as well as a discussion of the conditions under which phenylcyanamide ligands autodimerize. Infrared 15 N-isotope labeling experiments strongly suggest that phenylcyanamide ligands coordinate «end-on» by the nitrile nitrogen