Synthesis and structure of mixed ligand isonitroso-β-ketoiminenickel(II) complexes. Crystal structure of (1-ethoxycarbonyl-2-npropylimino-1-propanoneoximato) (1-methoxycarbonyl-2-imino-1-propanoneoximato)nickel(II)

Mixed ligand complexes of the type Ni(R-AB)(AC') and Ni(R-AC)(AB') where AB/AC denote N-bonded isonitroso- [3-ketoimino ligands, AB'/AC' denote the corresponding Obonded ligands and R = Me, Et, n-Pr are synthesised and characterised. The complexes are neutral with square planar geometry around nickel(II). The bonding isomerism of the isonitroso group is discussed on the basis of i.r. and 1H n.m.r. studies. The crystal structure of the title complex, Ni(n-Pr-IEAI)(IMAI') has been determined from diffractometer data by Patterson and Fourier methods and refined by least squares to R = 0.088 for 2209 observed reflections. Unit cell constants are: a = 11.945(2), b = 22.436(7), c = 13.248(5) ~, [3 = 95.13(2) ~ The space group is P2Jc with Z = 8. Niekel(II) has a square planar coordination of two imine nitrogens, an isonitroso-nitrogen (from n-Pr-IEAI) and another isonitrosooxygen (from IMAI').

Preparation and properties of nickel(II) complex dyes

The preparation and properties of five new dyes derived from nickel(I1) ions and aromatic azo derivatives of ethylenebls(P-ketoesters) are reported.

Coordination Behaviour of Imino Hydrazone Ligands towards Nickel (II) and Copper (II) Ions

The complexing ability of a new series of ligands, β-N-arylimine hydrazones, toward Ni (II) and Cu (II) ions has been studied. The isolated complexes are characterised on the basis of elemental analysis, spectroscopic methods and magnetic susceptibility measurements. The ligands are notentially bidentate in character coordinating to divalent metal ions through the N1 and N5 nitrogens. Square planar geometry of the metal ions is suggested on the basis of experimental evidence.

Infrared spectral assignments of methyl and ethyl xanthato complexes of nickel(II)

Assignments of the infrared frequencies of methyl and ethyl xanthato complexes of nickel(II) have been made with the aid of normal coordinate analyses. The assignments are discussed in relation to those in related molecules.

Ambidentate coordination of isonitrosoacetylacetone imines in their nickel(II) and palladium(II) complexes

Nickel(I1) and palladium(I1) complexes of the types Ni(R-IAI)(IAI'), Pd(IAI)(IAI'), and Pd(R-IAI), , where IAI and IAI' represent isonitrosoacetylacetone imine and R-IAI represents its Aralkyl derivative, have been prepared. The molar conductance, molecular weight, magnetic moment, and ir, pmr, and electronic spectra of these com- plexes have been studied. It is suggested that the isonitroso group of R-IAI coordinates through the nitrogen and that of IAI' thiough the oxygen in Ni(R-IAI)(IAI'). In Pd(R-IAI), the isonitroso groups of both ligands coordinate through nitrogen while Pd(IAI)(IAI') has a structure similar to that of Ni(R-IAI)(IAI'). The amine- exchange reactions of nickel(I1) and palladium(I1) complexes are discussed and compared on the basis of their structures.

Bromination of Intermolecular Chelate Linkage Isomers of 3-Oximino-4,9-Dimethyl (or 4,7,9-Trimethyl)-5,8-Diazadodeca-4,8-Diene-2,11-Dionato Nickel(II)

The reaction of the title complexes (FIG. 1) with N-bromosuccinimide or bromine in chloroform yields isomeric bromo complexes on substitution of the γ-CH carbon proton by bromine. The brominated products have been characterised by ir, pmr, electronic absorption spectra, conductivity and magnetic susceptibility measurements. The linkage isomerisation of the brominated products in chloroform has been shown to depend on the diamine residue.

Linkage isomerism in nickel(II) I-isonitroso-imine ligand complexes

I-isonitroso-imine ligand complexes of nickel(II), namely, bis(isonitrosomethylacetoacetate-imino)Ni(II), Ni(IMI)(IMI); bis(isonitrosobenzoylacetoneimino)Ni(II), Ni(IBI)(IBI) and bis(isonitrosoacetoacetanilideimino)Ni(II), Ni(IANI)(IANI), have been prepared and characterized. On the basis of their spectroscopic and magnetic properties, these complexes are suggested to have a square-planar stereochemistry around the metal ion with both nitrogen (ligand denoted without prime) and oxygen (ligand denoted with prime) coordinated isonitroso groups. The i.r. and NMR spectra of these and other similar complexes are discussed.

Structure of bis(thiocyanato-N)bis(thiosemicarbazide-N1,S)nickel(II): a redetermination

[Ni(NCS)2(CHsN3S)2], Mr = 356.7, monoclinic, P21/c , a = 5-297 (1), b = 7.869 (1), c - 16-078 (2) A,/3 = 91.53 (1) °, V-= 669.9 A 3, Z= 2, Om = 1"76, Dx = 1"771 g cm -3, A(Mo Ka) = 0-71069 ]k, /.~ = 19"9 cm-l, F(000) = 364, T = 295 K, final R = 0.026 for 1576 significant [F > 10g(F)] reflections. The complex lies on a crystallographic centre of symmetry. The Ni atom is octahedrally coordinated by two thiocyanates (through N atoms) and by two thiosemicarbazide molecules (through hydrazinic N and S atoms). The crystal structure is stabilized by N--H...S hydrogen bonds. Early work on this structure [Garaj & Dunaj-Jurco (1968). Chem. Commun. p. 518] used photographic data and was refined to R = 0-13 for 512 reflections.

Nitrosation of N,N′-ethylenebis-(acetylacetoneimine) complexes of copper (II) and nickel(II) and characterization of the products

Isonitroso derivatives of copper(II) and nickel(II) complexes of N,N′-ethylenebis(acetylacetoneimine) have been prepared by nitrosation of the respective complexes using nitric oxide as well as nitrite ion. The condensation of isonitrosoacetylacetone in the presence and in the absence of nickel(II) has been investigated. The i.r. and electronic spectra and magnetic moment of the nickel(II) and copper(II) complexes have been studied. The nature of bonding of the ligand to the metal ion is discussed. The complexes have planar structures.

Nickel(II) complexes of 1-benzyl-2-phenylbenzimidazole

Nickel(II) complexes of 1-benzyl-2-phenylbenzimidazole (BPBI) of the general formula [Ni(BPBI)2X2](X=Cl-, Br-, NCS- or NO3-) have been prepared and their magnetic moments, i.r. and electronic spectra studied. [Ni(BPBI)2Cl2] has a pseudotetrahedral structure while [Ni(BPBI)2 Br2] exists as square planar and speudotetrahedral isomers. [Ni(BPBI)2I2] and [NI(BPBI)2(NCS)2] have square planar stereochemistry. The nitrato complex [Ni(BPBI)2(NO)3)2] exists in two different octahedral modifications in the solid state.

Reactions of coordinated bivalent tetradentate schiff-base chelates of nickel (II) and palladium (II)

Reactions of N,N′-n-propylene-bis(acetylacetoneimino) metal (II), M[n-P-(AI)2], where M=Ni(II) or Pd(II), with nitrosating reagents have been investigated. Mono- and di-nitrosated complexes were obtained selectively, depending upon the concentration of the nitrosating reagents and the reaction time. In both the cases, the γ-CH group is transformed to an ambidentate isonitroso group (>C=NOH), which coordinates to the metal ion by dislodging the already coordinated carbonyl group. The factors influencing the mode of binding of the isonitroso group have been discussed. The bromination reactions of the mono-nitrosated products of M[n-P-(AI)2] and Pd (II) complexes, Pd [E/i-P-(AI)2], where E/i-P-(AI)2 is a dianion of ethylene/i-propylene-bis (acetylacetoneimine), are also reported. The reaction products have been characterized by elemental analyses, electrical conductivity molecular weight determination, and ir, pmr and electronic spectral data.

Cobalt(II), nickel(II) and copper(II) complexes of bidentate bibenzimidazoles

Complexes of cobalt(II), nickel(II) and copper(II) with novel bidentate bibenzimidazoles, [M(L-L)Cl2], where L-L are methylenebis(1, 1prime-benzimidazole), methylenebis(2, 2prime-benzimidazole) and dimethylenebis(2, 2prime-benzimidazole) are described and characterized by different physical measurements. The four coordinate complexes have distorted tetrahedral or square coplanar structures. The bridging entity between the two donor groups apparently influences the ligand field strength and the ligands occupy a higher position than that of benzimidazole in the spectrochemical series.