Reaction of substituted sulfenes with N,N-disubstituted α-amino-methyleneketones. I. Synthesis of N,N-disubstituted cis- and trans-4-amino-3,4,5,6,7,8-hexahydro-3-phenyl-1,2-benzoxathiin 2,2-dioxides

The polar 1, 4-cycloaddition of phenylsulfene (generated in situ from phenylmethanesulfony] chloride and triethylamine) to N, N-disubstituted (E)-2-aminomethylenecyclohexanones I gave in general a mixture of N, N-disubstituted cis- and trans-4-amino-3, 4, 5, 6, 7, 8-hexahydro-3-phenyl-1, 2-benzoxathiin 2, 2-dioxides III and IV, which were separated by column chromatography and whose structural and conformational features were determined from uv, ir and nmr spectral data. In the case of N, N-diisopropylamino enaminone 1c, the cyclo-addition took place with elimination of an alkyl group as propene to give the adduct III?.     

Diphosphacarbollide analogues of the C5H5- anion: isolation of the nido-di- and triphosphacarboranes 7,8,9-P2CB8H10, [7,8,9-P2CB8H9]-, [7,8,10-P2CB8H9]-, and 7,8,9,10-P3CB7H8

Treatment of a solution of excess PCl(3) and PS (PS = "proton sponge" = 1,8-dimethylamino naphthalene) with arachno-4-CB(8)H(14) (1) in CH(2)Cl(2), followed by hydrolysis of the reaction mixture, resulted in the isolation of the eleven-vertex diphosphacarbaborane nido-7,8,9-P(2)CB(8)H(10) (2) (yield 34%) as the main product. Other products isolated from this reaction were the phosphacarboranes nido-7,8,9,10-P(3)CB(7)H(8) (3) (yield 5%) and closo-2,1-PCB(8)H(9) (4) (yield 15%). Compound 2 can be deprotonated by PS in CH(2)Cl(2) or NaH in diethyl ether to give the [nido-7,8,9-P(2)CB(8)H(9)](-) (2(-)()) anion, which gives back the original compound, 2, upon re-protonation. Thermal rearrangement of anion 2(-) (Na(+) salt) at 350 degrees C for 2 h produced the isomeric [nido-7,8,10-P(2)CB(8)H(9)](-) (5(-)()) anion, which was isolated as a PPh(4)(+) salt (yield 86%). Multinuclear ((1)H, (11)B, (31)P, and (13)C), two-dimensional [(11)B-(11)B] COSY, (1)H{(11)B(selective)}, (1)H{(31)P(selective)}, and gradient-enhanced ([(1)H-(13)C] HSQC) magnetic resonance measurements led to complete assignments of all resonances which are in excellent agreement with the structures proposed. Coupling constants, (1)J((31)P,(13)C), (2)J((31)P,C,(1)H), and (1)J((31)P,(31)P), were calculated using the DFT method B3LYP/6-311+G(d,p). The molecular geometries of all compounds were optimized ab initio at a correlated level of theory (RMP2(fc)) using the 6-31G basis set, and their correctness was assessed by comparison of the experimental (11)B and (13)C chemical shifts with those calculated by the GIAO-SCF/II//RMP2(fc)/6-31G method. The computations also include the structures and chemical shieldings of the still unknown isomers [nido-7,10,8-P(2)CB(8)H(9)](-) (6(-)) and [nido-7,9,8-P(2)CB(8)H(9)](-) (7(-)).     

New insight into solvent effects on the formal HOO. + HOO. reaction

The 2,2'-azobis(isobutyronitrile)(AIBN)-induced autoxidation of gamma-terpinene (TH) at 50 degrees C produces p-cymene and hydrogen peroxide in a radical-chain reaction having HOO* as one of the chain-carrying radicals. The kinetics of this reaction in cyclohexane and tert-butyl alcohol show that chain termination involves the formal HOO. + HOO. self-reaction over a wide range of gamma-terpinene, AIBN, and O2 concentrations. However, in acetonitrile this termination process is accompanied by termination via the cross-reaction of the terpinenyl radical, T., with the HOO. radical under conditions of relatively high [TH] (140-1000 mM) and low [O2] (2.0-5.5 mM). This is because the formal HOO. + HOO. reaction is comparatively slow in acetonitrile (2k approximately 8 x 10(7) M(-1) s(-1)), whereas, this reaction is almost diffusion-controlled in tert-butyl alcohol and cyclohexane, 2k approximately 6.5 x 10(8) and 1.3 x 10(9) M(-1) s(-1), respectively. Three mechanisms for the bimolecular self-reaction of HOO. radicals are considered: 1) a head-to-tail hydrogen-atom transfer from one radical to the other, 2) a head-to-head reaction to form an intermediate tetroxide, and 3) an electron-transfer between HOO. and its conjugate base, the superoxide radical anion, O2-.. The rate constant for reaction by mechanism (1) is shown to be dependent on the hydrogen bond (HB) accepting ability of the solvent; that by mechanism (2) is shown to be too slow for this process to be of any importance; and that by mechanism (3) is dependent on the pH of the solvent and its ability to support ionization. Mechanism (3) was found to be the main termination process in tert-butyl alcohol and acetonitrile. In the gas phase, the rate constant for the HOO. + HOO. reaction (mechanism (1)) is about 1.8 x 10(9) M(-1) s(-1) but in water at pH< or =2 where the ionization of HOO. is completely suppressed, this rate constant is only 8.6 x 10(5) M(-1) s(-1). The very large retarding effect of water on this reaction has not previously been explained. We find that it can be quantitatively accounted for by using Abraham's HB acceptor parameter, beta(2)(H), for water of 0.38 and an estimated HB donor parameter, alpha(2)(H), for HOO. of about 0.87. These Abraham parameters allow us to predict a rate constant for the HOO. + HOO. reaction in water at 25 degrees C of 1.2 x 10(6) M(-1) s(-1) in excellent agreement with experiment.     

Intercalation of α,ω-alkyldiamines in layered α-zirconium phosphate and the inclusion behaviour of some of the intercalates obtained

The paper reports a study on the intercalation mechanism of NH₂(CH₂) _n NH₂ (withn=2, 4, 6, 8, 10) diamines in layered Zr(HOPO₃)₂·H₂O, performed by titrating the host with aqueous solutions of amines at 80°C. The intercalation reactions occur stepwise according to the ‘moving boundary’ model, with the formation of a number of intermediate intercalation compounds of formula Zr(HOPO₃)₂·xNH₂(CH₂) _n NH₂ (0<x<1) before obtaining the fully intercalated ones (x=1). For each diamine the batch titration curve and a diagram of the phases involved in the interaclation reaction are reported. Twenty-two intercalation compounds have been isolated and characterized by their composition, XRD patterns and thermal behaviour, and information on the disposition of the guests within the interlayer region have been derived. At full intercalation the diamines form a monolayer of extended molecules with their axis inclined at 58° to the plane of the sheet. The terminal amino groups are protonated by the —POH groups of the host, thus each diamine binds adjacent layers and, in a sense, transforms a layered structure into a framework structure that may have an accessible or potentially accessible porosity. The intercalation compound Zr(HOPO₃)₂·0.5NH₂(CH₂)₈NH₂ is indeed able to include polar molecules such as water and short chain alkanols.     

Models of the low-spin iron(III) hydroperoxide intermediate of heme oxygenase: magnetic resonance evidence for thermodynamic stabilization of the d(xy) electronic state at ambient temperatures

The (13)C pulsed ENDOR and NMR study of [meso-(13)C-TPPFe(OCH(3))(OO(t)Bu)](-) performed in this work shows that although the unpaired electron in low-spin ferrihemes containing a ROO(-) ligand resides in a d(pi) orbital at 8 K, the d(xy) electron configuration is favored at physiological temperatures. The variable temperature NMR spectra indicate a dynamic situation in which a heme with a d(pi) electron configuration and planar porphyrinate ring is in equilibrium with a d(xy) electron configuration that has a ruffled porphyrin ring. Because of the similarity in the EPR spectra of the hydroperoxide complexes of heme oxygenase, cytochrome P450, and the model heme complex reported herein, it is possible that these two electron configurations and ring conformations may also exist in equilibrium in the enzymatic systems. The ruffled porphyrinate ring would aid the attack of the terminal oxygen of the hydroperoxide intermediate of heme oxygenase (HO) on the meso-carbon, and the large spin density at the meso-carbons of a d(xy) electron configuration heme suggests the possibility of a radical mechanism for HO. The dynamic equilibrium between the ruffled (d(xy)) and planar (d(pi)) conformers observed in the model complexes also suggests that a flexible heme binding cavity may be an important structural motif for heme oxygenase activity.     

On the electronic states of macrocycles of the extended porphyrin family and their coordination compounds

The electronic absorption spectra of Ni, Zn and Mg hemiporphyrazine derivatives are presented and discussed together with theoretical results obtained by INDO/S computations. The absorption spectra of all the metal derivatives show marked red shifts of the lowest energy absorption bands with respect to those of the metal free hemiporphyrazine. The possible explanation that in metal derivatives low lying excited states with a fully conjugated π electron system are present is supported by theoretical computations.     

Reaction of sulfene and dichloroketene with open-chain N,N-disubstituted α-aminomethyleneketones. Synthesis of 4-dialkylamino-3,4-dihydro-5,6-dimethyl-1,2-oxathiin 2,2-dioxides and of 6,(5)(di)alkyl-3-chloro-4-methylphenylamino-2H-pyran-2-ones

Cycloaddition of sulfene to N,N-disubstituted 4-amino-3-methyl-3-buten-2-ones (III) occurred in fair to good yield only in the case of aliphatic N-substitution to give 4-dialkylamino-3,4-dihydro-5,6-dimethyl-1,2-oxathiin 2,2-dioxides, whereas N,N-disubstituted 1-amino-1-penten-3-ones (II) did not react at all. Cycloaddition of dichloroketene to II, III and N,N-disubstituted 4-amino-3-buten-2-ones occurred only in the case of the methylphenylamino derivative, giving in good to moderate yield 6,(5)(di)alkyl-3,3-dichloro-3,4-dihydro-4-methylphenylamino-2-Hpyran-2-ones, which were dehydrochlorinated with DBN to 6,(5)(di)alkyl-3-chloro-4-methylphenylamino-2H-pyran-2-ones.     

Structural researches on metal complexes with ligands containing the pyridoxal moiety: X-ray structure of chloro(N-pyridoxylidene-N′-salicyloylhydrazinato) copper(II) Monohydrate

Summary The x-ray crystal structure of the title complex is described Crystals are monoclinic, space groupP2₁/n, with unit-cell dimensions:a=18.070(2),b=13.471(2),c=6.788(2) Å,=94.70(1),Z=4. The structure was solved from diffractometer data by Patterson and Fourier methods and refined by least-squares techniques toR=5.0% for 2451 independent reflections. It consists of complex molecules, in which the copper atom square planar coordination comprises the chlorine atom, Cu-Cl=2.240(3) Å, and the organic ligand which acts as terdentate through the oxygen atom [Cu-O=1.948(3) Å] and a nitrogen atom, [Cu-N=1.933(5) Å] from the hydrazidic chain and the oxygen atom, [Cu-O = 1.894(4) Å] from the pyridoxal group.     

Two isomeric phosphacarboranes 2,1- and 6,1-PCB(8)H(9), the first representatives of the 10-vertex closo phosphacarborane Series

The reaction between arachno-4-CB(8)H(14) and PCl(3) in the presence of PS (PS = proton sponge = 1,8-dimethylamino naphthalene) (dichloromethane, rt, 24 h) produced the neutral phosphacarborane closo-2,1-PCB(8)H(9) (35% yield), while a similar reaction of nido-1-CB(8)H(12) gave the isomeric compound closo-6,1-PCB(8)H(9) (27% yield). The structures of both compounds were derived on the basis of the combined ab initio/GIAO/NMR ((1)H, (11)B, (13)C) approach. The optimized structures at a correlated level of theory (MP2) with 6-31G* basis set were used as a basis for calculations of the (11)B and (13)C chemical shifts at GIAO-SCF/II and GIAO-MP2/II, the latter showing excellent agreement with experimental data.     

Electrochemistry of coordination compounds: XIII. Ruthenium(I) and ruthenium(0) complexes generated by electrochemical reduction of chlorodi-(1,3-bisdiphenylphosphinopropane)ruthenium(II)-hexafluorophosphate

The electrochemical reduction of chlorodi-(1,3-bisdiphenylphosphinopropane)ruthenium(II)hexafluorophosphate, [RuCl(DPP)₂](PF₆), has been studied on the mercury electrode in 1,2-dimethoxyethane +0.1 M TBAP. The polarogram shows two reversible one-electron waves corresponding to the formation of [RuCl(DPP)₂] and [RuCl(DPP)₂]. Both products are unstable and decay through a disproportionation pathway and a fast internal metalation via Cl^? elimination with formation of HRu(C₆H₄PPh·CH₂CH₂ CH₂·PPh₂)(DPP), respectively. The hypothesis is put forward that the geometry of a metal-complex can be one of the factors which allow us to obtain d⁷ monomeric complexes by electrochemical methods.