Electronic structure and bonding of transition metal complexes MCO (MCu,Fe, Ti)

SCF-CI calculations with pseudopotentials using the CIPSI iterative algorithm have been carried out for various properties of CuCO, FeCO and TiCO complexes such as geometries, dissociation energies, dipole moments, force constants and vibration frequencies. These observables are compared to experimental data available for corresponding triatomic systems and, possibly, for chemisorbed CO. Their variations from Cu to Fe and Ti are rationalized in terms of σ donation and π back-donation effects computed from the molecular charge distribution.     

Electronic structure and energy decomposition of binuclear transition metal complexes containing β-diketiminate and imido ligands: spin state and metal’s nature effects

DFT calculations with full geometry optimization using BP86-D and OPBE functionals have been performed on series of [(BDI)M(NH)]₂(Bz) and [(BDI)M(NH)]₂(Tol) (M = Ti, V, Nb, Cr, Mn, Fe, Co, and Ni; BDI = β-diketiminate; NH = imido group; Bz = benzene; and Tol = toluene) of various spin states (singlet S = 0, triplet S = 1, quintet S = 2, and singlet S = 0 of broken symmetry method). Depending on the metal nature and its electron count and the spin state, the six-membered ring in [(BDI)M(NH)]₂(Bz) and [(BDI)M(NH)]₂(Tol) adopts various hapticities that involve full or partial coordination, giving rise to a flat or a distorted ring, respectively. The NH^2? imido group is linear or bent with respect to its sp or sp² hybridization acting as a six- or a four-electron donor, respectively. The (BDI)^? anion is a bidentate ligand as a six-electron donor. The optimized geometries do not show direct metal-metal bonding and correspond to long separations. The optimized structures for Nb metal are comparable to the available experimental ones. The Ziegler-Rauk energy decomposition analysis scheme was employed to characterize the geometry distortion, the steric interaction (electrostatic and Pauli), and the orbital interaction terms in the total bonding energy. The results showed that the interaction terms in all the studied complexes are governed by one third covalent and two thirds ionic characters, which are in agreement with the ΔE_elstat (electrostatic) and ΔE_orb (orbital) contributions, respectively, into the total attractive interaction (ΔE_elstat + ΔE_orb).     

Synthesis,structure and reactivity of complexes containing a transition metal–bismuth bond

The transition metal chemistry of bismuth has attracted significant interest since the 1970s. The low cost and high abundance of bismuth(III) reagents, such as the trihalides, makes them ideal starting materials and the size of the bismuth centre allows three- and higher-coordinate complexes to be synthesised, in which the bismuth atom is linked to one or more transition metal fragments. The ability to vary these metal fragments gives access to a plethora of available structures, with cyclopentadienylcarbonyl, metal carbonyl and sandwich compounds of bismuth in existence. Significant recent study has focused on applications in catalysis, where bismuth species can act as cross-coupling agents in carbon–carbon, carbon–nitrogen and carbon–oxygen bond forming reactions. Another striking feature is the variation in bonding situations that can be observed when studying the organometallic chemistry of bismuth. For example, dative and covalent interactions have been reported, in addition to cases of dibismuth acting as a two-, four- or six-electron donating ligand. This review aims to demonstrate the multi-faceted nature of the transition metal chemistry of bismuth and provide a detailed coverage of this topic.     

Reactions of transition metal σ-acetylide complexes: IX. Preparation and properties of some cycloheptatrienylvinylidene complexes

Addition of [C₇H₇][PF₆] to iron, ruthenium or osmium alkynyl complexes has given eight cationic cycloheptatrienylvinylidene derivatives [M{C C(C₇H₇)R}(L)₂ (η-C₅H₅)][PF₆] (M = Fe, Ru or Os; R = Me, Pr, Ph or C₆F₅; L = PPh₃, L₂ = dppm or dppe; but not all combinations). With Fe(C₂Ph)(CO)₂(η-C₅H₅), only [Fe(CO)₂(thf)(η-C₅H₅)][PF₆] was obtained. Reactions of the new complexes are characterised by loss of the C₇H₇ group. The NMR spectra and FAB mass spectra are described in detail.     

Metallophosphoranes: The hidden face of transition metal–phosphine complexes

Reactions in which metallophosphoranes, of general formula L_nMPR₄, have been implicated as intermediates or possible transition states are reviewed. Such species can be accessed via nucleophilic attack on metal–phosphine complexes, with the source of nucleophile being either external or internal in the form of an anionic co-ligand. The reverse process, transfer of a group from a {PR₄} ligand to a metal, has also been observed with the formation of a metal phosphine. Thus metallophosphoranes have been postulated to play a role in isomerization processes and novel M–X/P–R exchange reactions. Metallophosphoranes have also been implicated in unusual ‘phosphine-assisted C–F bond activation’ reactions. Recent computational studies on these processes are discussed.     

Syntheses and crystal structures of transition metal complexes of 1,1′-bisacetylacetoferrocene

Bimetallic complexes 3a–e of 1,1′-bisacetylacetoferrocene (2) were prepared by reactions of transition metal acetates M(OAc)₂ (M?=?Co²⁺, Mn²⁺, Cu²⁺, Ni²⁺, Zn²⁺) with the 2 in refluxing methanol. The X-ray structures of the cobalt and manganese complexes were determined showing very similar centrosymmetric macrocyclic dimeric frameworks constituted by linkage of two Co²⁺ or Mn²⁺ ions and two 1,1′-diacetoacetylferrocene units with two additional methanols as bridges dividing this macrocyclic framework into two small cyclic subunits. The UV-Vis spectra and electronic properties were also studied.     

Reactions of transition metal σ-acetylides: VIII. Preparation and properties of some aryldiazo-vinylidene complexes

Fourteen aryldiazovinylidene complexes of ruthenium and osmium have been made by addition of aryldiazonium cations to the appropriate σ-acetylides. Their properties and spectra (including FAB-MS) are described, and reactions with MeOH, hydride and methoxide are reported. Addition to and protonation, alkylation, and cyclomanganation of the aryldiazo functions are also described.     

The i.r. spectra of ethylenediamine complexes—I. The tris(ethylenediamine) complexes of first transition series metal(II) sulphates

The i.r. spectra of the complex [Zn(en)₃]SO₄ and its ⁶⁴Zn-, ⁶⁸Zn-, ¹⁵N-, N₂D₄- and C₂D₄-labelled analogues have been determined over the range 4000-50 cm⁻¹. Band assignments are based on the isotopically induced shifts and also those which result from substitution of Zn(II) by the metal(II) ions of the first transition series: Mn(II), Fe(II), Co(II), Ni(II) and Cu(II). The spectrum of the Cu(II) complex yields evidence of Jahn—Teller distortion.     

The metal complexes of amino acids and their N-substituted derivatives—VI. The physical properties,i.r. spectra and normal coordinate analysis of bivalent metal complexes with dl-threonine

Complexes of five bivalent metals with dl-threonine have been prepared and characterized by means of i.r. absorption, powder diffuse reflection, and electronic spectra, X-ray diffraction and magnetic susceptibility. The complexes appear to be of three distinct types. The first type includes ML₂·nH₂O (M = Ni, Cu, Zn; L = dl-threoninato anion), in which the ligand chelates metal ions through the nitrogen atom and the oxygen atom of the carboxylato group. Three species of copper(II) complexes have been prepared. They seem to be two trans forms and one cis form. MnCl₂(HL)₄·H₂O is a second type in which the metal is coordinated through the oxygen atom of the carboxyl group and chloride ions, but is not coordinated through the nitrogen atom. 2CdCl₂·HL·HCl·2H₂O is a third type, in which the metal is coordinated through only chloride ions. In order to assign the observed frequencies of i.r. absorption spectra in detail, a normal coordinate analysis has been accomplished for the complexes of the first type as a 33-body problem. Copper(II) and zinc(II) complexes with l-threonine have been prepared for comparison.     

Photophysics of π-conjugated oligomers and polymers that contain transition metal complexes

There has been a surge of interest concerning the synthesis, optical and electronic properties of π-conjugated polymers that contain transition metal complexes. The integration of transition metal chromophores that feature metal to ligand charge transfer (MLCT) excited states into a π-conjugated polymer permits easy variation of the material’s optical and electronic properties. In this review, we survey a number of recent photophysical studies that examine π-conjugated oligomer or polymer/transition metal complex hybrids. The effects of the types of π-conjugated backbone, oligomer and polymer structure, the conjugation length and coordination to a variety of metal chromophores on the photophysics of the organic-metal hybrids are discussed. The degree of interaction between the polymer (or oligomer) and metal complex based excited states dramatically modulates the observed photophysics.     

The metal complexes of heterocyclic β-diketones and their derivatives—VI. The synthesis,structure and i.r. spectral studies of some new metal(II) complexes of 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP)

The monovalent metal complex of Na and the divalent metal complexes of Be, Mn, Co, Ni, Cu, Zn, Mg, Ba, Hg and Pb with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP), have been synthesized. It is shown that HPMBP behaves like a bidentate enol forming neutral metal chelates through the carbonyl and enolic hydroxyl groups. Characterization of the complexes were by means of elemental analyses, conductivity measurements, i.r. and proton NMR spectroscopy. The i.r. spectra were recorded between 4000 and 200 cm⁻¹ and assignments are proposed for the observed frequencies. Replacement of the methyl group of the 4-acetyl moiety by the phenyl group in the metal chelates of 1-phenyl-3-methyl-4-acetyl-pyrazolone-5 (HPMAP), is found to decrease the C

O, C

C and MO stretching frequencies of the chelate ring. The magnitudes of the MO stretching frequencies for the transition metals show good agreement with the Irving—Williams stability order Cu>Ni>Co>Zn>Mn.     

N-picolinamido-N′-benzoylthiocarbamide transition metal complexes

A new series of CoII, NiII and CuII complexes derived from N-picolinamido-N-benzoylthiocarbamide has been prepared in which the Schiff base ligand is tridentate and/or bidentate, containing a potential ONS donor. The complexes have been characterized by elemental analyses, 1H-n.m.r., magnetic susceptibility, i.r., u.v., e.p.r. and thermal analyses. Stereochemistries are proposed for the complexes on the basis of the spectral and magnetic studies. The i.r. data indicate that the carbonyl oxygen of the benzoyl moiety constituents chelating backbone in most complexes.     

Mössbauer spectra of ferrous salts of transition metal cyano complexes. A survey

Ferrous salts of ten hexacyanometallates and three tetracyanometallates were obtained and their Mössbauer spectra interpreted according to recent structural models for these families of compounds. Ferrous ferrocyanide (Williamson White) and its ruthenium and osmium analogs prepared mechanochemically are stable for hours, allowing their study by Mössbauer spectroscopy and other related techniques. For ferrous salts of trivalent hexacyanometallate anions, the random distribution of anion vacancies is discarded and a model of two well defined relative positions of CN and H2O ligands around the Fe2+ is suggested. Iron was found octahedrally coordinated in tetracyanometallates.     

Indenyl and fluorenyl transition metal complexes: XIV. Synthesis and reactions of chromium tricarbonyl complexes of 5,10-dihydroindeno[2,1-α]indene

1-4,4a,10b-η⁶-5,10-dihydroindeno[2,1-α]indene chromium tricarbonyl (III) has been obtained by Rausch's method. Deprotonation of III by t-BuOK in THF solution, by potassium solution in HMPTA or by KH in THF at −65°C yields an η⁶-anion IV, which is irreversibly rearranged into η⁵-anion V at 20°C. Action of n-BuLi/t-BuOK mixture in THF at −65°C results in the formation of η⁶-dianion VI, which is irreversibly converted into η⁵-dianion VII above 0°C. Alkylation of IV with benzyl iodide yields 5-exo-benzyl(III). Reaction of V with benzyl iodide leads to the σ-benzyl derivative, which is isomerized into 5-endo-benzyl(III). The reaction of V with N-nitroso-N-methyltosylamide yields the η⁵-nitrosodicarbonyl complex of chromium (XI).     

Synthesis, characterization, and antifungal studies of transition metal complexes of ω-bromoacetoacetanilide isonicotinylhydrazone

Isonicotinic acid hydrazide or isonicotinylhydrazide, commonly known as isoniazid, is an antibacterial agent that has been used to treat tuberculosis. It interacts with microbial cell walls. Schiff’s bases or anils are the compounds having >C=N−N< linkages, which have immense applications as catalysts, stabilizers, pigments, dyes, and drugs. They have good ability to form chelates with many metal ions. Isoniazid can form Schiff’s bases with diketones such as acetoacetanilide. Acetoacetanilide isonicotinylhydrazone and its metal chelates exhibit anticancer activity. Our studies on N-methyl-acetoacetanilide isonicotinylhydrazone and its metal chelates revealed that they are active against pathogenic fungal strains. Hence, it is worthwhile to synthesize new complexes of ligands having different substituents on the acetoacetanilide moiety. We synthesized five new metal chelates of ω-bromoacetoacetanilide isonicotinylhydrazone. The ligand behaved as a tridentate monoanion or as a tridentate dianion in the complexes. These compounds were characterized mainly by elemental analysis; conductivity measurements; and electronic, infrared, and nuclear magnetic resonance spectral studies. We also carried out antifungal studies of these compounds against four selected pathogenic fungal strains using a cup-plate technique. Both the ligand and its metal chelates were active against all fungal strains investigated. However, the chelates were found to be more active than the ligand.     

Physical organic chemistry of transition metal carbene complexes. 24. Thermodynamic and kinetic acidities of phenyl-substituted (benzylmethoxycarbene)pentacarbonylchromium(0) complexes. Is there a transition-state imbalance?

A kinetic study of the reversible deprotonation of phenyl-substituted (benzylmethoxycarbene)pentacarbonylchromium(0) complexes by OH(-) and by a series of primary aliphatic and a series of secondary alicyclic amines in 50% MeCN-50% water (v/v) at 25 degrees C is reported. Br?nsted alpha(CH) values (dependence on carbene complex acidity) and beta(B) values (dependence on amine basicity) were determined. According to current notions about proton transfers involving carbon acids activated by pi-acceptors, alpha(CH) was expected to substantially exceed beta(B), the result of transition-state imbalances that are characteristic of such reactions. However we find that alpha(CH) and beta(B) have essentially the same values, which are close to 0.5. It is shown that these findings do not indicate the absence of an imbalance but rather suggest that the manifestation of the imbalance is masked by the pi-donor effect (3H-Z <--> 3H-Z(+/-)) of the methoxy group.     

N-Ferrocenylcarbonyl-N′-benzoylhydrazine and its transition metal(II) complexes

Summary A new ferrocene derivative, N-ferrocenylcarbonyl-N-benzoylhydrazine (H₂FB) and its transition metal complexes, [M(FB)]₂·H₂O (M = Mn^II, Co^II, Cu^II, Zn^II, Cd^II or Hg^II) and M(HFB)₂·nH₂O (M = Mn^II or Cd^II) were prepared by reacting H₂FB with the metal(II) acetates and characterized by elemental analyses, i.r. and u.v. spectroscopy and t.g.a. H₂FB appears to act as a tetradentate ligand, coordinating to the metal through the nitrogen enolic oxygen atoms.     

Construction of M–M bonds in late transition metal complexes

The 16-electron Co, Rh and Ir half-sandwich complexes of Cp^#M[E₂C₂(B₁₀H₁₀)] and Cp^#M(E₂S₂C₆H₄) (M = Co, Rh, Ir, Ru; E = S, Se) containing chelating 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolato ligands and benzenedithiolato ligands are promising precursors to build multimetallic clusters by reactions with low oxidation state late transition metal reagents. Such reactions lead to successful constructions of M–M bonds between iridium, rhodium, cobalt, ruthenium, and other late transition metals. Most of these complexes have been characterized by X-ray single crystal determinations and some have been studied by computational methods. Such theoretical studies reveal the covalent bonding nature of those multinuclear complexes. Some of these clusters have been found to have interesting nonlinear optical properties.