I. Nickel Research Articles

Crystal structure of a new mixed-metal coordin-ation polymer consisting of NiII piperidine-di-thio-carbamate and penta-nuclear CuI-I cluster units.

A new heterometallic CuI-NiII coordination polymer, poly[[tetra-μ3-iodido-μ2-iodido-bis-(μ3-piperidine-1-di-thio-carbamato)propio-nitrilepenta-copper(I)nickel(II)] chloro-form monosolvate], {[CuI5NiIII5(C6H10NS2)2(C3H5N)]·CHCl3} n , has been synthesized and structurally characterized. This coordination polymer consists of an NiII mononuclear unit of NiII(Pip-dtc)2 (Pip-dtc- is piperidine-1-di-thio-carbamate) and a penta-nuclear copper(I) cluster unit of Cu5I5(CH3CH2CN). The NiII ion, which lies on an inversion centre, is surrounded by four S atoms in a square-planar coordination geometry while all CuI ions have distorted tetra-hedral coordination geometries. In the penta-nuclear copper(I) cluster unit, a mirror plane passes through one CuI ion and three I ions. All the S atoms in NiII(Pip-dtc) are also coordinated by the CuI ions, forming an infinite zigzag chain structure along the b-axis direction. The chains are weakly connected by solvent CHCl3 mol-ecules via Cl⋯I [3.653 (1) Å] and Cl⋯S [3.4370 (1) Å] short-contact inter-actions.

Three different functions of a phosphinic amidato ligand inLNi(LLi)(LH) {L= [tBu2P(O)NEt]−}

The title paramagnetic compound, chloro-2κCl-[di-tert-butyl­phos­phinic ethylamide-1κO]­bis­[μ-di-tert-butyl­phos­phin­ic ethyl­amidato(1−)-1:2κ4O:N]­lithium(I)­nickel(II), [NiLiCl(C10H23NOP)2(C10H24NOP)], revealed an incomplete bischelation of Ni2+ by L− {L = [tBu2P(O)NEt]−}, with the formation of a pseudo-tetrahedral NiON2Cl chromophore. The Ni atom is coordinated by Cl−, bidentate L− and mono­dentate LLi (via N).

Infrared, Raman, resonance Raman spectra and lattice dynamics calculations of the solid potassium(I) nickel(II) thiophosphate compound, KNiPS4

Abstract The UV-visible (350–850 nm), infrared and Raman (20–700 cm−1) spectra of a new KNiPS4 solid compound have been analyzed using powder samples and crystalline platelets. From polarization measurements, the main electronic transition of 1F2←1A1 type due to the PS43− thiophosphate groups are localized in the 360–570 nm range and vibrational assignments for most of the fundamental modes are proposed. These assignments were checked by complete valence force field lattice dynamics calculations in the various symmetry blocks of the tetragonal crystal structure (D4h14). Potential energy distributions as well as mean squared vibrational amplitude calculations have shown strong ν(NiS) and σ(SPS) couplings in the (NiPS4)− structural chains and remarkably high ν(NiS) infrared frequencies. Furthermore, the resonance Raman spectra of single crystals and powder samples were recorded over a wide range (647.1-476.5 nm) of excitatiob wavelengths. This allowed to probe the nature of the broad electronic transition of the complex centered around 510 nm and responsible for KNiPS4 brown color. The Raman excitation profiles of several fundamentals and combination bands were thus established. Under resonance conditions, various crystalline components of A1g, B1g and B2g symmetry for the ν4(F2) or ν2(E) deformation modes of the PS43− groups are enhanced. No overtone progressions involving totally symmetric modes were observed but anomalously intense high-order combination bands were detected. It is thus concluded that adiabatic as well as non-adiabatic interactions must play a great role in the vibronically induced Raman scattering processes. Reasons for this peculiar behavior are discussed in relation to the X-ray crystal structure of the KNiPS4 compound. All the experimental results imply the presence of substantial site and factor group effects on the optical and vibronic properties of the thiophosphate anions.

Transition metal complexes with the thiosemicarbazide-based ligands—I. Nickel(II) complexes with the quadridentate ligands based on S-methylisothiosemicarbazide; X-ray crystal structure of (acetyl-acetone N(1)-salicylidene-S-methylizothiosemicarbazonato) nickel(II)

The reaction of a warm ethanolic solution of [Ni(SALSMeTSC-H)Py]Cl·0.5Py (SALSMeTSC = salicylaldehyde S-methylisothiosemicarbazone) with salicylaldehyde and acetylacetone (HACAC), yielded the corresponding square-planar complexes [Ni(SAL 2SMeTSC-2H)] ( A) and [Ni(SALACACSMeTSC-2H)] ( B) (SAL 2SMeTSC, and SALACACSMeTSC = quadridentate 2O2N ligand: N(1),N(3)- bis(salicylidene)-S-methylisothiosemicarbazide, and acetylacetone N(1)-salicylidene-S-methylisothiosemicarbazone, respectively). An X-ray analysis of complex B showed that in the reaction of the starting complex with HACAC a rearrangement of the salicylaldehyde moiety takes place (while the CN(3) bond of the azomethine group is ruptured) and its binding to the N(1) nitrogen. At the same time, HACAC is simultaneously bonded to the liberated N(3)-nitrogen of the hydrazine fragment. Crystal data for the complex B (NiC 14H 15N 3O 2S) are: M r = 348.0, orthorhombic, space group Pna2 1, a = 7.484(3), b = 21.995(8), c = 8.866(3) Å; V = 1459.44 Å 3, Z = 4, F(000) = 720, Dc = 1.58 g cm −1, Do = 1.56 g cm −1, μ(MoKα) = 14.45 cm −1. The structure was solved by the heavy-atom method and refined anisotropically to an R value of 0.078 for 1174 non-zero reflections. The complex molecules are planar, the NiNi distance of nearest molecules being about 3.76 Å. The compounds have been characterized by elemental analysis as well as by IR and electronic spectra.

Metal complexes of pyrimidine-derived ligands—I: Nickel(II) complexes of 2-hydrazino-4,6-dimethyl pyrimidine

Bis- and tris-Ni(II) complexes of 2-hydrazino-4,6-dimethyl pyrimidine(L) are reported: they are of the type NiL 2X 2· nH 2O and NiL 3X 3· nH 2O (X Cl, Br, I, NO 3, ClO 4, BF 4 and n = 0 or 2). Their structures are deduced from reflectance spectra, visible spectra in solution, IR spectra, magnetic susceptibility measurements in the solid state and conductivity measurements in solution. The magnetic data for all the complexes indicate, a 3 A 2 g ground state for the nickel(II) ion in a magnetically dilute, essentially octahedral environment. The electronic spectra suggest an octahedral configuration in the majority of the complexes; NiL 2Br 2·2H 2O and NiL 2I 2·2H 2O are somewhat tetragonal. IR spectra indicate tentatively the mode of linkage of the ligand molecules and the anion (X) to the metal ion in the complexes in the solid state.

Nitrogen-oxygen donor macrocyclic ligands. I. Nickel(II) complexes of a new series of cyclic ligands derived from salicylaldehydes

Nitrogen-oxygen donor macrocyclic ligands. I. Nickel(II) complexes of a new series of cyclic ligands derived from salicylaldehydes

Thin-layer chromatographic separation of diphenylthiovioluric acid chelates

Work on diphenylthiovioluric acid (DPHTVA) has shown that chelates formed by this reagent are extractable into various organic solvents. This has been made the basis of separation by TLC. Spectrophotometric determinations of iron (III), ruthenium (III) with DPHTVA have been recently reported [ 1-2]. Owing to the extractability of a large number of metalDPHTVA chelates, DPHTVA cannot be used as a selective reagent. In the present study, ions known to form DPHTVA chelates have been grouped bearing in mind, as far possible group similarity or the ability to form extractable DPHTVA chelates in the same pH range. The constituents of such groups of ions have been separated using TLC. Groups of ions investigated are: (i) Nickel (II), cobalt (II), copper (II) and iron (III). (ii) Ruthenium (III), platinum (IV) and palladium (II).

Transition metal complexes of organo-thiophosphorus ligands. I. Nickel(II) chelates of some new diphenylthiophosphinyl thioureas

Some new diphenylthiophosphinyl thioureas Ph 2P(S)NHC(S)NR′R″ (R′ = H, R″ = α- and β-naphthyl, m-tolyl and NR′R″ = piperidyl) were prepared. They form nickel(II) chelates, which have been characterized by infrared and electronic spectra. Two isomeric forms of β-naphthyl derivatives were isolated, both showing anomalous magnetic behaviour. The electronic structure of the chelate ring is discussed on the basis of infrared spectral data.

Absolute configuration of coordination compounds. I. Nickel(II) and zinc(II) complexes of PAPY [HPAPY = 1-(2'pyridyl)-3-(6''-methyl-2''-pyridyl)1,2-diaza-2-propene

Absolute configuration of coordination compounds. I. Nickel(II) and zinc(II) complexes of PAPY [HPAPY = 1-(2'pyridyl)-3-(6''-methyl-2''-pyridyl)1,2-diaza-2-propene

Alkyl- and aryl-fluorophosphines as ligands in transition-metal complexes with metals in positive oxidation states. Part I. Nickel(II) and cobalt(II) halide complexes of di-(t-butyl)fluorophosphine

Di-(t-butyl)fluorophosphine forms stable complexes of the type NiX2L2 and CoX2L2(where X = Cl, Br, or I and L = But2PF) with nickel(II) and cobalt(II) halides. The structure of these compounds, elucidated by n.m.r., i.r., and u.v. spectra as well as by magnetic measurements is trans-square planar in the case of NiX2L2 and tetrahedral for the complexes CoX2L2. For NiCl2(But2PF)2 a cis-trans-equilibrium is likely to exist in solution. The low-temperature 19F n.m.r. spectrum of the latter compound is explained by the presence of different rotamers with respect to the Ni–P axis.

Pentadentate ligands. I. Nickel(II) complexes of the linear Schiff base ligands derived from substituted salicylaldehydes and diethylenetriamine and 2,2'-bis(aminopropyl)amine

Pentadentate ligands. I. Nickel(II) complexes of the linear Schiff base ligands derived from substituted salicylaldehydes and diethylenetriamine and 2,2'-bis(aminopropyl)amine

Metal complexes as indicators for solvent structure. Part I. Nickel(II) complexes of meso-stilbenediamine or triethylenetetramine in mixed aqueous media

The electronic spectra of solutions of salts of either the triethylenetetraminenickel(II) ions on the bis-m-stilbenediaminenickel(II) ion have been used to measure the ratio of the blue form (B) to the yellow form (Y) under various conditions (mixed solvents, added salts, temperature). log [Y]/[B] is proportional to a defined solvent molarity, and appears to give a method of evaluating structure-making (e.g. proteins) or breaking (e.g. urea) agents.

Metal complexes of N,N,N',N'-tetramethyldiamines. I. Nickel(II) and cobalt(II) complexes

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMetal complexes of N,N,N',N'-tetramethyldiamines. I. Nickel(II) and cobalt(II) complexesLuigi Sacconi, I. Bertini, and F. ManiCite this: Inorg. Chem. 1967, 6, 2, 262–267Publication Date (Print):February 1, 1967Publication History Published online1 May 2002Published inissue 1 February 1967https://doi.org/10.1021/ic50048a015RIGHTS & PERMISSIONSArticle Views428Altmetric-Citations70LEARN 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 (688 KB) Get e-Alerts Get e-Alerts

Arylamine co-ordination complexes. Part I. Nickel(II) complexes containing uni- and bi-dentate o-phenylenediamine and 4-methyl-o-phenylenediamine

Download options Please wait... Article information DOI https://doi.org/10.1039/J19670001464 Article type Paper Download Citation J. Chem. Soc. A, 1967, 1464-1469 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions Arylamine co-ordination complexes. Part I. Nickel(II) complexes containing uni- and bi-dentate o-phenylenediamine and 4-methyl-o-phenylenediamine D. R. Marks, D. J. Phillips and J. P. Redfern, J. Chem. Soc. A, 1967, 1464 DOI: 10.1039/J19670001464 To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Search articles by author D. R. Marks D. J. Phillips J. P. Redfern