Dimeric 5-coordinate oxovanadium(IV) complexes of tridentate benzoyl hydrazones

The oxovanadium(IV) complexes of the hydrazones derived from benzoylhydrazine and salicylaldehyde (BSH), o-hydroxyacetophenone (BAH), o-hydroxypropiophenone (BPH), o-hydroxybutyrophenone (BBH) and 2-hydroxy-1-naphthaldehyde (BNH) have been described. These complexes have been characterised by elemental analyses and by molecular weight, conductance, magnetic, IR and electronic spectral measurements. The IR spectra suggest the presence of phenoxide bridging and thus the complexes are formulated as dimers, each unit having 5-coordinate distorted square-pyramidal geometry. The low μ_eff values (1.02 – 1.26 B.M.) have been attributed to antiferromagnetic exchange coupling and the principal path for spin coupling is direct σ-metal-metal interaction. The electronic spectra have been interpreted in terms of energy level scheme delineated for distorted square-pyramidal geometry. Various ligand field parameters Dq, Ds, Dt along with NSH parameters DQ, DS and DT have been evaluated and the degree of distortion (DT/DQ) lies in the range 0.169 – 0.233.     

Reactions of 5-, 6-, 7-, 8-hydroxyquinolines and 5-hydroxyisoquinoline with benzene and cyclohexane in superacids

Isomeric 5-, 6-, 7-hydroxyquinolines (11-13) and 5-hydroxyisoquinoline (14) gave N,C-diprotonated dications in CF(3)SO(3)H-SbF(5) superacid medium. Compounds 11, 13, 14, and 8-hydroxyquinoline (5) underwent selective ionic hydrogenation with cyclohexane in the presence of aluminum chloride. Compounds 11 and 14 condense with benzene in the presence of aluminum halides. The detailed mechanism of reactions, which involves superelectrophilic dicationic intermediates, is discussed.     

Synthesis and characterization of titanium (IV) Schiff base complexes,part III1. Octahedral titanium (IV) complexes of some dibasic terdentate Schiff base ligands

Summary Complexes of the X₂Ti(SB) type, where X is OMe, OEt and OPr-i and SB is the dianion of salicylaldehyde-2-hydroxyanil (H₂SAP), acetylacetone-2-hydroxyanil (H₂AAP) and acetylacetone-2-mercaptoanil (H₂ASP), have been prepared and characterized by means of conductivity, molecular weight, i.r., n.m.r and mass spectral measurements. The ONO and ONS donor ligands are terdentate and the titanium(IV) atom attains six-coordinationvia dimerization of the complexes. The tendency of (i-PrO)₂Ti(AAP), where AAP is the dianion of acetylacetone-2-hydroxyanil, to become monomeric and to disproportionate to Ti(AAP)₂ and Ti(OPr-i)₄ was also investigated. Spectral data are also presented for the octahedral complexes of the Ti(SB)₂ type, where SB is the dianion of H₂SAP, H₂AAP, H₂ASP or of the related ONO donor ligands salicylaldehyde-2-hydroxyethylimine (H₂SAE), salicylaldehyde-3-hydroxypropylimine (H₂SPA), and diisopropylethanolamine (H₂DIP).Presented in part at the 166th ACS National Meeting, Chicago, Illinois, Aug. 26–31, 1973; No. INORG. 50.     

Preparation and characterisation of some stereochemically rigid 7-coordinate mono-methylcyclopentadienyl zirconium(IV) tris-N,N-dialkyl dithiocarbamate complexes

Zirconium(IV) N,N-dialkyl dithiocarbamates of the type MeCnZr(S₂CNR₂)₃ where R = Me, Et have been prepared by reaction of bis-methycyclopentadienyl zirconium(IV) dichloride with sodium salts of substituted dithiocarbamic acids in aqueous and non-aqueous media. They have also been prepared by reaction of mono-methycyclopentadienyl zirconium(IV) trichloride with sodium salts of substituted dithiocarbamic acids in non-aqueous medium. Molecular weight, conductance and IR studies point out that these complexes are monomeric non-electrolytes in which all of the dithiocarbamate ligands are bidentate. Therefore, a coordination number “7” may be assigned to zirconium(IV) ion in these compounds. Proton NMR spectra of these complexes in carbon disulfide or deuterated chloroform indicate that (i) there is hindered rotation about CN bonds at ambient temperature, and (ii) metal centered rearrangement is slow on the NMR time-scale at ambient temperature (30°C).     

Indium tri(isopropoxide)-catalyzed selective Meerwein-Ponndorf-Verley reduction of aliphatic and aromatic aldehydes

Indium tri(isopropoxide)-catalyzed Meerwein-Ponndorf-Verley reduction of aliphatic and aromatic aldehydes in 2-propanol gave selectively the corresponding primary alcohols in good to excellent yields at room temperature. A wide range of functional groups including alkene, ether, ketone, ester, nitrile, and nitro were tolerated under the optimum reaction conditions. Chemoselective reductions were also achieved not only between aromatic aldehyde, aromatic ketone, and epoxide but also between aliphatic aldehyde and alkene.     

Rhodium(II) catalyzed multi-component reactions of aryldiazoacetates with titanium(IV) isopropoxide and imines

Rh₂(OAc)₄ catalyzed diazo decomposition of aryldiazoacetates in the presence of titanium(IV) isopropoxide generated oxonium ylide intermediates. Trapping of the oxonium ylide intermediates with imines occurred subsequently via a nucleophilic addition. The three-component reaction of aryldiazoacetates, titanium(IV) isopropoxide, and imines gave α-alkoxyl-β-amino acid derivatives with C-N/C-C bond formation in a single step. Extension of the study to a four-component reaction with in situ generated imine was also investigated.     

Tin(IV), titanium(IV) and hafnium(IV) complexes of some aromatic Schiff bases derived from 4-aminoantipyrine

Summary Tin(IV), titanium(IV) and hafnium(IV) chloride complexes of ligands such as salicylidene-4-aminoantipyrine (HL¹), 5-chlorosalicylidene-4-aminoantipyrine (HL²), 2,4-dihydroxybenzylidene-4-aminoantipyrine (HL³), 2-hydroxy-1-naphthylidene-4-aminoantipyrine (HL⁴) and 2-hydroxyacetophenonylidene-4-aminoantipyrine (HL⁵) have been prepared and characterized. The analytical data show that tin(IV) forms only 1:1 metal complexes when reacted with HL¹, HL³ and HL⁴, whereas it forms 1:1 and 1:2 metal complexes when reacted with HL², depending on the molar ratio. HL⁵ produces only the binuclear complex SnHL⁵Cl₄(H₂O)SnCl₄. Titanium(IV) gives only one type of complex of the general formula [Ti(HL)₂Cl₂]Cl₂-2H₂O, whilst hafnium(IV) gives HfHL³Cl₄-4H₂O and Hf(L⁵)₂Cl₂.     

Heavy-metal aromatic rings: cyclopentadienyl anion analogues Sn5(6-) and Pb5(6-) in the Zintl Phases Na8BaPb6, Na8BaSn6, and Na8EuSn6

The title compounds were prepared by direct reactions of the corresponding elements at high temperature. They are isostructural with each other (monoclinic, P2(1)/m, Z = 2; Na(8)BaPb(6), a = 13.116(4), b = 5.351(1), and c = 16.166(5) A, beta = 108.07(2) degrees; Na(8)BaSn(6), a = 12.897(4), b = 5.362(1), and c = 16.826(5) A, beta = 108.19(2) degrees; Na(8)EuSn(6), a = 12.912(2), b = 5.220(1), and c = 15.721(2) A, beta = 108.09(1) degrees ) and contain isolated, flat, and aromatic pentagonal rings of Sn(5)(6)(-) and Pb(5)(6)(-) as well as isolated anions of Sn(4)(-) and Pb(4)(-). According to four-probe conductivity measurements, the tin compounds, Na(8)BaSn(6) and Na(8)EuSn(6), are semiconducting with band gaps of 0.11 and 0.09 eV, respectively, and are therefore electronically balanced. Magnetic measurements show that Na(8)BaSn(6) is diamagnetic while Na(8)EuSn(6) is paramagnetic and undergoes two transitions at low temperatures.     

Multicomponent reactions involving p-benzoquinones, diazo esters, titanium(IV) isopropoxide and alcohol in the presence of rhodium(II) acetate as catalyst

A Rh₂(OAc)₄ catalyst derived oxonium ylide intermediate underwent nucleophilic addition with the CC or CO bond of p-benzoquinones. The syntheses of 2-substituted hydroquinones and 1-hydroxy-4-oxocyclohexa-2,5-dienyls have been demonstrated.     

Reactions of aliphatic,aromatic, and heterocyclic aminothiols with diacetylene

Reactions of aliphatic, aromatic, and heterocyclic aminothiols with diacetylene in liquid ammonia or methanol furnished the corresponding aminoorganylsulfanylbutenynes of predominantly Z-configuration.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 11, 2004, pp. 1725–1727.Original Russian Text Copyright © 2004 by Volkov, Volkova.     

Carbon-13-nuclear magnetic resonance spectra of 5-coordinate tris-olefin complexes of rhodium(I)

Studies of the ¹³C N.M.R. spectra of the series RhX[P(Ch₂CH₂CHCH₂)₃] and RhX[P(CH₂CH₂CH₂CHCH₂)₃] where x  Cl or Br have revealed that (a) the J(¹⁰³Rh-¹³C) (olefin) for the complexes studied is only $\text{1}\text{2}$ ? $\text{1}\text{3}$ that found for square-planar complexes, and (b) the fluxional character in the olefinic carbons observed for the compounds RhX[P(CH₂CH₂CHCH₂)₃] is related to the partial rotation of the olefin about the rhodium-olefin bond.     

Dinuclear Cu(I) complexes of 1,2,4,5-tetra(7-azaindolyl)benzene: persistent 3-coordinate geometry, luminescence, and reactivity

Five Cu(I) complexes [Cu2(ttab)(CH3CN)2][BF4]2 (1), [Cu(2)(ttab)(PPh3)2][BF4]2 (2), [Cu2(ttab)I2] (3), [Cu2(ttab)(I3)2] (4), and [Cu2(ttab)(I)BF4]n (5) with 1,2,4,5-tetra(7-azaindolyl)benzene (ttab) have been synthesized and characterized. The structures of compound 1, 2, 4, and 5 have been determined by single-crystal X-ray diffraction analyses, which established that 1, 2, and 4 are discrete dinuclear Cu2 compounds while compound 5 is a 1D coordination polymer with the I- ligand bridging two dinuclear Cu2 units. The ttab ligand in all four complexes adopts a 1,3-chelation mode. The Cu(I) center in all complexes is three-coordinate. Close contact between the Cu(I) center and the benzene ring in the ttab ligand was observed in all four structures, which is believed to play a role in stabilizing the three-coordinate geometry of the Cu(I) center. The crystals of 1, 2, and 5 contain channels in the lattice that host solvent molecules such as CH2Cl2 and toluene. Fluorescent measurements established that, in solution, compounds 1-3 display weak blue luminescence which originates from the ttab but is significantly red-shifted and has a much lower emission intensity, compared to the free ttab ligand. The application of compound 1 in C-N cross-coupling reactions was examined by using the reaction of phenyl halides with imidazole as a model system. For the reaction with phenyl iodide, 1 was found to be as effective a catalyst as the CuI/1,10-phenanthroline system. For the reaction with phenyl bromide, 1 is less effective than the CuI/1,10-phenanthroline system. Compound 1 reacts with O2 gas, as established by UV-vis spectra, but the oxidized products have not been characterized.     

Reactions of 6-benzyl-5-methyl-2-(methylsulfanyl)pyrimidin-4(3H)-one with aliphatic and aliphatic-aromatic amines

Russian Journal of Organic Chemistry - The rules were investigated of the regioselective synthesis of N2-substituted derivatives of 2-amino-6-benzyl-5-methylpyrimidin-4(3H)-one from...     

Steric control of coordination number: A series of Mo(VI) dioxo diaryloxide complexes bearing 4-, 5-, and 6-coordinate environments

The design, synthesis, and structure determination of a series of Mo(VI) dioxo diaryloxide complexes have been reported. By varying the steric bulk of the aryloxide ligand, control of the coordination number around the Mo(VI) center was achieved. All the complexes are characterized by analytical and spectroscopic techniques. Preliminary reactivity tests indicate that the 4-coordinate compound is the most stable and the 6-coordinate compound is the least stable.     

Highly luminescent complexes [Mo6X8(n-C3F7COO)6]2- (X=Br, I)

New complexes (Bu(4)N)(2)[Mo(6)X(8)(n-C(3)F(7)COO)(6)] (X = Br, I) display extraordinarily bright long-lived red phosphorescence both in solution and solid phases, with the highest emission quantum yields and the longest emission lifetimes among hexanuclear metal cluster complexes of Mo, W and Re, hitherto reported.     

Reactions of trichloro(cyclopentadienyl)titanium(IV) with 1,5-diarylthiocarbazones

Summary The synthesis and characterization of the complexes from the reactions of trichloro(cyclopentadienyl)titanium(IV) with 1,5-diarylthiocarbazones (aryl=phenyl,o-tolyl,o-chlorophenyl,p-tolyl,p-chlorophenyl, or 3,5-dimethylphenyl) are reported. They are of the types CpTi(HDz)Cl₂ and CpTi(HDz)₂Cl (Cp=cyclopentadienyl, HDz^–=the mono-anion of a 1,5-diarylthiocarbazone, H₂Dz). The compounds are nonelectrolytes in dimethylformamide (DMF). In solid state, the far i.r. spectra of CpTi(HDz)Cl₂ indicate the complexes to be dimeric, involving Cl-bridges.     

Reactions of 1-alkynylphosphonates with group (IV) complexes

This article describes our recent methods for the synthesis of substituted vinylphosphonates by reacting 1-alkynylphosphnates with group (IV) complexes. cis-Vinylphosphonates, 1,3-butadienylphosphonates, 1-(hydroxymethyl)vinylphosphonates, 2-(hydroxymethyl)vinylphosphonates, (E) 3-oxo-1-alkenylphosphonates were produced as a result of the reactions between zirconium complexes and 1-alkynylphosphonates. On the other hand, titanium complexes afford 3-aminovinylphoshonates, 1,4-bis-phosphonates, and various other di- and tri-substituted vinylphosphonates. An evaluation of access of these recently synthesized vinylphosphonates as MMP-2 inhibitors has shown that certain compounds are very potent and promising.