Reactions of Mixed-Valent Palladium (IV,II) Complexes of Tetradentate Schiff-Bases Involving Bond Isomerization

Reactions of [PdIVB-(AI)2]++ [PdIICl4]-- (i) B-(AI)2 = dianion of N,N'-ethylene-/i-propylene-/n-propylene-bis(acetyl-acetoneimine) with some π-acceptor ligands, aliphatic primary amines and nitrosating reagents have been investigated. In all these reactions except nitrosation, 1:1 adducts having the formula, [PdIVB-(AI)2.X] [PdIICl4] [X = triphenylphosphine (TPP), triphenylarsine (TPA), pyridine (Py), methylamine (CH3NH2) or ethylamine (C2H5NH2)] are obtained. The formation of these complexes is associated with a bond isomerization - from Pd-Cxo-π -allylic bond prevailing in [PdIVB-(AI)2]2+ to PdIV-O bonding.Reaction of (i) with nitrosating reagents reduces PdIV to PdII and subsequently transform the γ-CH group, into an ambidentate isonitroso group (°C = NOH). The latter enters into coordination with PdII by dislodging the already coordinated carbonyl group. Further, selective nitrosation (mono- and dinitrosation) has been carried out by controlling the amount of the nitrosating reagent and the reaction time. The complexes have been characterized by elemental analyses, electrical conductivity, magnetic susceptibility and ir spectral data.

Syntheses, X-ray structure and properties of (5-cyclopentadienyl)ruthenium(II) complexes of pyridyl-2-hydrazone ligands

Complexes of the formulae [(-Cp)Ru(PPh3)(2-PPH)]Cl and [(Cp)Ru(PPh3) (py)(1-PPH)]Cl were prepared by reacting pyridyl-2-phenylhydrazone [PPH, C5H4N-2-CH=NNHPh] with (-Cp)Ru(PPh3)2Cl and (-Cp)Ru(PPh3)(py)Cl, respectively. In these complexes the PPH ligand displays bidentate chelating and unidentate modes of bonding. The molecular structure of [(-Cp)Ru(PPh3)(2-PPH)](ClO4)·CH2Cl2 was determined by X-ray crystallography. In this complex the metal is bonded to the N-pyridyl and N-imine atoms of the chelating ligand. 1H NMR spectral data suggests that PPH is bonded to ruthenium through the pyridine moiety of the PPH ligand in [(η-Cp)Ru(PPh3)(py)(η1-PPH)]Cl.

Synthesis, spectral and structural studies on metal complexes of Schiff bases involving vitamin B6 and histamine

Six metal complexes of Schiff bases involving Vitamin B6 and the decarboxylated amino acid histamine have been synthesised and characterized. Crystal structures have been determined for [CuL1(H2O)Br]-NO31(L1= pyridoxylidenehistamine) and [Cu2L22(NO3)2]·6H2O 2(L2= 5′-phosphopyridoxylidenehistaminate). The crystal structure of complex 1[space group P[1 with combining macron], a= 8.161(2), b= 10.368(2), c= 11.110(2)Å, α= 105.18(1), β= 102.12(1), γ= 72.10(1)° and Z= 2; R= 0.072, R′= 0.083] consists of square-pyramidally co-ordinated copper with the tridentate Schiff base in the zwitterionic form, whereas in 2[space group P[1 with combining macron], a= 8.727(1), b= 10.308(1), c= 12.845(2)Å, α= 110.00(1), β= 78.94(1), γ= 114.35(1)° and Z= 1; R= 0.035, R′= 0.034] the copper has the same co-ordination geometry but the tetradentate Schiff-base ligand exists as a monoanion. The conformational parameters deduced from such structures are important for understanding the stereochemical aspects of Vitamin B6-catalysed model reactions involving histidine.

Pes study of spin-state transitions in d6 transition metal complexes and oxides

Transitions from the low-to the high-spin state in Fe2+ and Co3+ compounds have been examined by X-ray and UV photoelectron spectroscopy. It has been shown that the core-level bands in XPES, in particular the metal 3s band, as well as the valence bands, are diagnosis in the study of spin-state transitions.

The crystal and molecular structure of putrescine - di-glutamic acid complexes

The polyamines spermine, spermidine, putrescine, cadaverine, etc. have been implicated in a variety of cellular functions. However, details of their mode of interaction with other ubiquitous biomolecules is not known. We have solved a few structures of polyamine-amino acid complexes to understand the nature and mode of their interactions. Here we report the structure of a complex of putrescine with DL-glutamic acid. Comparison of the structure with the structure of putrescine-L-glutamic acid complex reveals the high degree of similarity in the mode of interaction in the two complexes. Despite the presence of a centre of symmetry in the present case, the arrangement of molecules is strikingly similar to the L-glutamic acid complex.

X-ray studies on crystalline complexes involving amino acids and peptides XIX. Effects of change in chirality in the complexes of succinic acid with dl- and l-arginine

Crystals of dl-arginine hemisuccinate dihydrate (I)(monoclinic; P21/c; a = 5.292, b = 16.296, c = 15.203 Å; α= 92.89°; Z = 4) and l-arginine hemisuccinate hemisuccinic acid monohydrate (II) (triclinic; P1; a = 5.099; b = 10.222, c = 14.626 Å; α= 77.31, β= 89.46, γ= 78.42°; Z = 2) were grown under identical conditions from aqueous solutions of the components in molar proportions. The structures were solved by direct methods and refined to R = 0.068 for 2585 observed reflections in the case of (I) and R = 0.036 for 2154 observed reflections in the case of (11). Two of the three crystallographically independent arginine molecules in the complexes have conformations different from those observed so far in the crystal structures containing arginine. The succinic acid molecules and the succinate ions in the structures are centrosymmetric and planar. The crystal structure of (II) is highly pseudosymmetric. Arginine-succinate interactions in both the complexes involve specific guanidyl-carboxylate interactions. The basic elements of aggregation in both the structures are ribbons made up of alternating arginine dimers and succinate ions. However, the ribbons pack in different ways in the two structures. (II) presents an interesting case in which two ionisation states of the same molecule coexist in a crystal. The two complexes provide a good example of the effect of change in chirality on stoichiometry, conformation, aggregation, and ionisation state in the solid state.

X-ray studies on crystalline complexes involving amino acids and peptides. XXI. Structure of a (1:1) complex between L-phenylalanine and D-valine

CsHllNO2.C9HilNO2, Mr = 282.3, P1, a = 5.245 (1), b = 5.424 (1), c = 14.414 (2) A, a = 97.86 (1), fl = 93-69 (2), y = 70-48 (2) °, V= 356 A 3, Z = 1, O m = 1-32 (2), Dx = 1.32 g cm-3, h(Mo Ka) = 0-7107 A, g = 5-9 cm-1, F(000) = 158, T= 298 K, R=0.035 for 1518 observed reflections with I>2tr(I). The molecules aggregate in double layers, one ayer made up of L-phenylalanine molecules and the other of D-valine molecules. Each double layer is stabilized by interactions involving main-chain atoms of both types of molecules. The interactions include hydrogen bonds which give rise to two head-to-tail sequences. The arrangement of molecules in the complex is almost the same as that in the structure of DL-valine (and DL-leucine and DL-isoleucine) except for the change in the side chain of L molecules. The molecules in crystals containing an equal number of L and O hydrophobic amino-acid molecules thus appear to aggregate in a similar fashion, irrespective of the precise details of the side chain.

X-ray studies on crystalline complexes involving amino acids and peptides. XXV. Structures of DL-proline hemisuccinic acid and glycyl-L-histidinium semisuccinate monohydrate and a comparative study of amino-acid and peptide complexes of succinic acid

DL-Proline hemisuccinic acid, C5H9NO2.1/2C4H6O4, M(r) = 174.2, P2(1/c) a = 5.254 (1), b = 17.480 (1), c = 10.230 (i) angstrom, beta = 119.60 (6)-degrees Z = 4, D(m) = 1.41 (4), D(x) = 1.42 g cm-3, R = 0.045 for 973 observed reflections. Glycyl-L-histidinium semisuccinate monohydrate, C8H13N4O3+.C4H5O4-.H2O, M(r) = 348.4, P2(1), a = 4.864 (1), b = 17.071 (2), c = 9.397 (1) angstrom, beta = 90.58-degrees, Z = 2, D(m) = 1.45 (1), D(x) = 1.48 g cm-3, R = 0.027 for 1610 observed reflections. Normal amino-acid and dipeptide aggregation patterns are preserved in the structures in spite of the presence of succinic acid/semisuccinate ions. In both the structures, the amino-acid/dipeptide layers stack in such a way that the succinic acid molecules/semisuccinate ions are enclosed in voids created during stacking. Substantial variability in the ionization state and the stoichiometry is observed in amino-acid and peptide complexes of succinic acid. Succinic acid molecules and succinate ions appear to prefer a planar centro-symmetric conformation with the two carboxyl (carboxylate) groups trans with respect to the central C=C bond. Considerable variation is seen in the departure from and modification of normal amino-acid aggregation patterns produced by the presence of succinic acid. Some of the complexes can be described as inclusion compounds with the amino acid/dipeptide as the 'host' and succinic acid/semisuccinate/succinate as the 'guest'. The effects of change in chirality, though very substantial, are not the same in different pairs of complexes involving DL and L isomers of the same amino acid.

Mechanistic Aspects of Nucleophilic Substitution at Half-Sandwich Metal Complexes

The hydrolysis reactions of organometallic ruthenium(II) piano-stool complexes of the type Ru-II(eta(6)-cymene)(L)Cl](0/+) (1-5, where L = kappa(1)- or kappa(2)-1,1-bis(diphenylphosphino)methane,1,1bis-(diphenylphosphino)methane oxide, kappa(1)-mercaptobenzothiazole) have been studied using density functional theory at the B3LYP level. In addition to considering a syn attack in an associative fashion, where the nucleophile approaches from the same side as the leaving group, we have explored alternative paths such as an anti attack in an associative manner, where the nucleophile attacks from the opposite side of the leaving group. During the anti attack, an intermediate is formed and there is a coordination mode change of the arene ring from eta(6) to eta(2) along with its rotation. When the intermediate goes to the product, the arene ring slips back from eta(2) to eta(6) coordination. This coordinated movement of the arene ring makes the associative anti attack an accessible pathway for the substitution process. Our calculations predict very similar activation barriers for both syn and anti attacks. In the dissociative path, the rate-determining step is the generation of a coordinatively unsaturated 16-electron ruthenium species. This turns out to be viable once solvent effects are included. The large size of the ancillary ligands on Ru makes the dissociative process as favorable as the associative process. Activation energy calculations reveal that although the dissociative path is favorable for kappa(1) complexes, both dissociative and associative processes can have significant contribution to the hydrolysis reaction in kappa(2) complexes. Once activated by hydrolysis, these complexes react with guanine and adenine bases of DNA. The thermodynamic stabilities of complexes formed with the nucleobases are also presented.

Mixed ligand cobalt(III) complexes of tetradentate N,N′-ethylenebis(acetylacetonimine) and flexidentate isonitroso-β-diketones and isonitrosomonoketones

A series of mixed ligand cobalt(III) complexes having the general formula Co(EA)X [where EA = dianion of N,N′-ethylenebis(acetylacetonimine) and X = anion of isonitroso-acetylacetone, IAA; isonitrosobenzoylacetone, IBA; isonitrosodibenzoylmethane, IDBM; isonitrosoethylacetoacetate, IEA; isonitrosoacetoacetanillide, IAN; isonitrosoethylmethylketone, IEMK; isonitrosobenzylmethylketone, IBMK and isonitrosopropiophenone, IPP] have been synthesised and characterised. A facial-cis-β structure (cis with respect to the coordinated two oxygen atoms of EA) with N,N,N,O,O,O ligational environment has been assigned for the complexes. The characterisation of the complexes has been based upon chemical analysis, electrical conductivity, magnetic moment, IR, PMR and electronic spectra.

Lanthanide perchlorate complexes of o,o' diisopropyl, n(-4-antipyryl) phosphoramidate

Five new complexes of lanthanide perchlorates with a new ligand O,O' diisopropyl N(-4-antipyryl) phosphoramidate (DIAP) of the general formula Ln(DIAP)4(ClO4)3 where Ln = La, Pr, Nd, Sm and Gd, have been synthesised and characterized by chemical analysis, IR(200–4000cm−1) and electronic spectra and electrical conductance data. Infrared spectral data indicate the coordination of the ligand to the metal ions in a bidentate fashion, through the C=O oxygen of the antipyrine group and the P=O group. IR and conductance values show that the three perchlorate groups are ionic. Electronic spectrum of the Nd3+ complex in the visible region, indicates reasonable covalency in the metal-ligand bond. The available data point to an eight coordinate geometry around the metal ions, with each ligand behaving in a bidentate ‘00’ fashion.

Donor properties of some flexidentate hydroxyimino-β-diketones in their rhodium(III) complexes

A series of rhodium(III) complexes of certain hydroxyimino-beta-diketones were synthesised and their structures assigned on the basis of elemental analyses and i.r. and1H n.m.r. spectral studies, The complexes exhibit coordination through carbonyl oxygen and nitrogen of the hydroxy-imino groups in the ligands.1H and13C n.m.r. studies show that the ligands exist in the isonitroso form in CDCl3.