Probing the nature of the Co(III) ion in corrins: a comparison of the thermodynamics and kinetics of the ligand substitution reactions of aquacyanocobyrinic acid heptamethyl ester and stable yellow aquacyanocobyrinic acid heptamethyl ester

Equilibrium constants (log K) for the substitution of coordinated H(2)O in aquacyanocobyrinic acid heptamethyl ester (aquacyanocobester, ACCbs) and stable yellow aquacyanocobyrinic acid heptamethyl ester (stable yellow aquacyanocobester, ACSYCbs), in which oxidation of the C5 carbon of the corrin interrupts the normal delocalized system of corrins, by ligands with soft (CN(-), SO(3)(2-), and S(2)O(3)(2-)) and hard (NO(2)(-) and N(3)(-)) donors have been determined. The ligands with a harder donor atom (N in N(3)(-) and NO(2)(-)) produce ΔH values that are more negative in their reactions with ACSYCbs than with ACCbs. If the donor atom is softer (C in CN(-) and S in SO(3)(2-)), then ΔH is less positive, or more negative, for reactions with ACCbs than with ACSYCbs. The softer metal in ACCbs has a preference for softer ligands and the harder metal in ACSYCbs for the harder ligands. A kinetics study in which CN(-) substitutes H(2)O on Co(III) shows that ACCbs is more labile than ACSYCbs; the second-order rate constant k(II) is between 4.6 (at 5 °C) and 2.6 (at 35 °C) times larger. ΔH(?) for the reaction of CN(-) with ACCbs is smaller by some 12 kJ mol(-1) than that for the reaction with ACSYCbs, consistent with an earlier transition state in which bonding between the softer metal of ACCbs and the ligand is greater than that of ACSYCbs with its harder metal. This difference in ΔH(?) makes ACCbs over 100 times more labile, although the effect is masked by a ΔS(?) value that is over 30 J K(-1) mol(-1) more negative. There is a significant increase in the inertness of Co(III) upon a decrease in the extent of conjugation of the corrin ligand. Modifying the electronic structure of the equatorial ligand in the cobalt corrins can modify the thermodynamics and kinetics of its reactions with exogenous ligands.     

Reduction of the double bonds in heptamethyl cycloheptatriene-1,2,3,4,5,6,7-heptacarboxylate

Hydrogenation of heptamethyl cycloheptatrieneheptacarboxylate in the presence of palladium/carbon affords a stereoisomer of heptamethyl cyclohepteneheptacarboxylate with the cis-position of five ester groups in a yield of 60%, as well as the corresponding cyclohepta-1,3-dienes as trans,trans- and trans,cis-isomers. The reaction with sodium borohydride results in the stereoselective formation of bicyclic compound 5 upon reduction of one double bond and intramolecular cyclization. X-ray diffraction analysis of the compounds formed is carried out.     

Photooxygenolytic Degradation of the Vitamin-B12 Derivative Heptamethyl Coα,Coβ-Dicyanocobyrinate. Efficient Preparation of Bicyclic Fragments

The methylene-blue sensitized photooxygenation of heptamethyl Coα,Coβ-dicyanocobyrinate ( 1 , cobester) at ca. ?45° and in (D₃)acetonitrile solution proceeds readily to the stage of selective double cleavage of the corrin macrocycle. It furnishes the bisected heptamethyl Coα,Coβ-dicyano-5,6:14,15-tetraoxo-5,6:14,15-disecocobyrinate ( 3 ) in 91% yield after warming the photooxygenation mixture to room temperature. Complex 3 is also obtained by photooxygenation of the secocorrinoid oxygenation products of 1 , namely of heptamethyl Coα,Coβ-dicyano-5,6-dioxo-5,6-secocobyrinate ( 2a ) and of its isomer heptamethyl Coα,Coβ-dicyano-14,15-dioxo-14,15-secocobyrinate ( 2b ). When the raw photooxygenation product of 1 is kept at low temperature, 3 is not formed in a significant amount; spectral analysis reveals 4 as intermediate that is transformed into 3 quantitatively upon warm-up and storage at r.t. Compound 4 is assigned the structure of heptamethyl Coα,Coβ-dicyano-5,6-epidioxy-5,6-dihydro-14,15-dioxo-14,15-secocobyrinate, based on NMR-spectral data and since 4 is also formed cleanly in the corresponding low-temperature photooxygenation of 2b . Catalytic reduction of the Co(III) complex 3 (H₂, Pt/C) in the presence of EDTA produces a colourless oil, from which the bicyclic fragments 5 (corresponding to rings A and D of 1 ) and 6 (corresponding to rings B and C of 1 ) are obtained in 99 and 91% yield, respectively, after chromatographic separation.     

Incoherent inelastic neutron scattering of the strong (NHN) bond in H3Co(CN)6

The vibrations of the strong symmetric NHN hydrogen bond in H₃Co(CN)₆ have been investigated by inelastic neutron scattering spectroscopy at 80 K. The two deformation modes δ(NH) and γ(NH) have been identified. A strong protonic mode is observed in the low energy transfer region and is assigned to the antisymmetric stretching vibration of the hydrogen bond. Relative intensities of the ν(NH) fundamental, its first overtone and bending fundamentals are interpreted as suggesting a strongly anisotropic Debye-waller factor. At 5 K the ν(NH) fundamental shows a complex structure which is interpreted in terms of coupling with low frequency lattice modes.     

Cyanation of aryl bromides with K4[Fe(CN)6] catalyzed by dichloro[bis{1-(dicyclohexylphosphanyl)piperidine}]palladium, a molecular source of nanoparticles, and the reactions involved in the catalyst-deactivation processes

Dichloro[bis{1-(dicyclohexylphosphanyl)piperidine}]palladium [(P{(NC(5)H(10))(C(6)H(11))(2)})(2)PdCl(2)] (1) is a highly active and generally applicable C-C cross-coupling catalyst. Apart from its high catalytic activity in Suzuki, Heck, and Negishi reactions, compound 1 also efficiently converted various electronically activated, nonactivated, and deactivated aryl bromides, which may contain fluoride atoms, trifluoromethane groups, nitriles, acetals, ketones, aldehydes, ethers, esters, amides, as well as heterocyclic aryl bromides, such as pyridines and their derivatives, or thiophenes into their respective aromatic nitriles with K(4)[Fe(CN)(6)] as a cyanating agent within 24 h in NMP at 140 °C in the presence of only 0.05 mol % catalyst. Catalyst-deactivation processes showed that excess cyanide efficiently affected the molecular mechanisms as well as inhibited the catalysis when nanoparticles were involved, owing to the formation of inactive cyanide complexes, such as [Pd(CN)(4)](2-), [(CN)(3)Pd(H)](2-), and [(CN)(3)Pd(Ar)](2-). Thus, the choice of cyanating agent is crucial for the success of the reaction because there is a sharp balance between the rate of cyanide production, efficient product formation, and catalyst poisoning. For example, whereas no product formation was obtained when cyanation reactions were examined with Zn(CN)(2) as the cyanating agent, aromatic nitriles were smoothly formed when hexacyanoferrate(II) was used instead. The reason for this striking difference in reactivity was due to the higher stability of hexacyanoferrate(II), which led to a lower rate of cyanide production, and hence, prevented catalyst-deactivation processes. This pathway was confirmed by the colorimetric detection of cyanides: whereas the conversion of β-solvato-α-cyanocobyrinic acid heptamethyl ester into dicyanocobyrinic acid heptamethyl ester indicated that the cyanide production of Zn(CN)(2) proceeded at 25 °C in NMP, reaction temperatures of >100 °C were required for cyanide production with K(4)[Fe(CN)(6)]. Mechanistic investigations demonstrate that palladium nanoparticles were the catalytically active form of compound 1.     

Factors affecting the solid-state structure and dimensionality of mercury cyanide/chloride double salts, and NMR characterization of coordination geometries

In the reaction of organic monocationic chlorides or coordinatively saturated metal-ligand complex chlorides with linear, neutral Hg(CN)(2) building blocks, the Lewis-acidic Hg(CN)(2) moieties accept the chloride ligands to form mercury cyanide/chloride double salt anions that in several cases form infinite 1-D and 2-D arrays. Thus, [PPN][Hg(CN)(2)Cl].H(2)O (1), [(n)Bu(4)N][Hg(CN)(2)Cl].0.5 H(2)O (2), and [Ni(terpy)(2)][Hg(CN)(2)Cl](2) (4) contain [Hg(CN)(2)Cl](2)(2-) anionic dimers ([PPN]Cl = bis(triphenylphosphoranylidene)ammonium chloride, [(n)Bu(4)N]Cl = tetrabutylammonium chloride, terpy = 2,2':6',6' '-terpyridine). [Cu(en)(2)][Hg(CN)(2)Cl](2) (5) is composed of alternating 1-D chloride-bridged [Hg(CN)(2)Cl](n)(n-) ladders and cationic columns of [Cu(en)(2)](2+) (en = ethylenediamine). When [Co(en)(3)]Cl(3) is reacted with 3 equiv of Hg(CN)(2), 1-D [[Hg(CN)(2)](2)Cl](n)(n-) ribbons and [Hg(CN)(2)Cl(2)](2-) moieties are formed; both form hydrogen bonds to [Co(en)(3)](3+) cations, yielding [Co(en)(3)][Hg(CN)(2)Cl(2)][[Hg(CN)(2)](2)Cl] (6). In [Co(NH(3))(6)](2)[Hg(CN)(2)](5)Cl(6).2H(2)O (7), [Co(NH(3))(6)](3+) cations and water molecules are sandwiched between chloride-bridged 2-D anionic [[Hg(CN)(2)](5)Cl(6)](n)(6n-) layers, which contain square cavities. The presence (or absence), number, and profile of hydrogen bond donor sites of the transition metal amine ligands were observed to strongly influence the structural motif and dimensionality adopted by the anionic double salt complex anions, while cation shape and cation charge had little effect. (199)Hg chemical shift tensors and (1)J((13)C,(199)Hg) values measured in selected compounds reveal that the NMR properties are dominated by the Hg(CN)(2) moiety, with little influence from the chloride bonding characteristics. delta(iso)((13)CN) values in the isolated dimers are remarkably sensitive to the local geometry.     

An investigation of the stability of the phosphate ester bond in D-pantothenic acid 4′-phosphate

The hydrolysis of the phosphate ester bond in D-pantothenic acid 4-phosphate in strongly acid (9 and 6 N HCl), weakly acid, weakly alkaline, and strongly alkaline (5 N KOH) aqueous media has been studied. In strongly acid and strongly alkaline media the phosphate ester bond of (I) breaks down completely in 3 and 2.5 h, respectively. The rate of hydrolysis at pH values between 1.3 and 11 remains constantly low but almost doubles in the presence of lanthanum salts at pH 8–9 and in the presence of lithium salts at pH 4 and a molar ratio of (I):Me⁺=1:1.Institute of Biochemistry Academy of Sciences of the Belorussian SSR, Grodno. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 262–265, March–April, 1987.     

Migratory insertion of hydrogen isocyanide in the pentacyano(methyl)cobaltate(III) anion

The preparation of the pentacyano(iminiumacetyl)cobaltate(III) anion and its N-methyl and N,N-dimethyl derivatives is reported. The iminiumacetyl group is formed by migratory insertion of cis hydrogen isocyanide in the pentacyano(methyl)cobaltate(III) anion. The new compounds have been spectroscopically characterized by (1)H, (13)C, (15)N, and (59)Co NMR spectroscopy and by absorption spectroscopy. The iminium carbon atoms yield (13)C NMR signals at 256.7, 247.7, and 240.4 ppm for the parent iminiumacetyl compound and its N-methyl and N,N-dimethyl derivatives, respectively. The (15)N resonance frequencies of the iminium groups and the lack of rotation of the carbon-nitrogen bond both show that this bond is best described as a double bond. The structure of (Et(4)N)(Ph(4)As)(2)[Co(CN)(5)(CH(3))] was determined by X-ray crystallography at 122.0(5) K. The structure displays disorder.     

Silver(I) and copper(I) complexes supported by fully fluorinated 1,3,5-triazapentadienyl ligands

Synthesis of the perfluorinated 1,3,5-triazapentadiene [N{(CF(3))C(C(6)F(5))N}(2)]H and the use of its conjugate base as a supporting ligand for the isolation of silver(i) and copper(i) complexes are reported. Some of the related chemistry involving [N{(C(3)F(7))C(C(6)F(5))N}(2)](-) (that has bulkier -C(3)F(7) groups on the 1,3,5-triazapentadienyl ligand backbone) is also presented. X-ray crystallographic data show a wide variety of structures ranging from intermolecular, hydrogen-bonded chain structure for [N{(CF(3))C(C(6)F(5))N}(2)]H with a twisted W-shaped N(3)C(2) core, monomeric [N{(CF(3))C(C(6)F(5))N}(2)]Ag(CN(t)Bu)(2) and [N{(C(3)F(7))C(C(6)F(5))N}(2)]Ag(CN(t)Bu)(2) where the κ(1)-bonded triazapentadienyl ligand bonding to the metal fragment via the central nitrogen atom, monomeric [N{(CF(3))C(C(6)F(5))N}(2)]Ag(PPh(3))(2) and [N{(C(3)F(7))C(C(6)F(5))N}(2)]Ag(PPh(3))(2) that feature κ(1)-bonded triazapentadienyl ligand bonding to the metal fragment via one of the terminal nitrogen atoms, to that of the monomeric [N{(CF(3))C(C(6)F(5))N}(2)]Cu(CN(t)Bu)(2) containing a κ(2)-bonded triazapentadienyl ligand and a U-shaped NCNCN ligand backbone. The isocyanide adducts show relatively high ν(CN) values in the IR spectra.     

Structural studies of metalloporphyrins. VI—13C relaxation time,T1, measurements and the nature of the axial N—metal bond in some macrocyclic complexes

Rotation barriers around the metal—pyridine bond of various macrocyclic complexes of cobalt(III), rhodium(III), zinc(II) and magnesium(II) have been studied using the ¹³C longitudinal relaxation times, T₁, of the carbon atoms of pyridine and the macrocycle. The data have been rationalized on the basis of steric and electronic factors. The influence of π back-donation on the rates of rotation around the axial Co? N and Rh? N bonds is discussed. The agreement found between the conclusions drawn from this study and X-ray data reported for complexes of identical or closely related structure demonstrates the validity of this method.     

Tetracyanomanganate(II) and its salts of divalent first-row transition metal ions

The first known paramagnetic, tetrahedral cyanide complex, [Mn(II)(CN)(4)](2)(-), is formed by the photoinduced decomposition of [Mn(IV)(CN)(6)](2)(-) in nonaqueous solutions or by thermal decomposition in the solid state. In acetonitrile or dichloromethane, photoexcitation into the ligand-to-metal charge transfer band (lambda(max) = 25 700 cm(-1), epsilon = 3700 cm(-1) M(-1)) causes the homolytic cleavage of cyanide radicals and reduction of Mn(IV). Free cyanide in dichloromethane leads to the isolation of polycyanide oligomers such as [C(12)N(12)](2)(-) and [C(4)N(4)](-), which was crystallographically characterized as the PPN(+) salt C(40)H(30)N(5)P(2): monoclinic space group = I2/a, a = 18.6314(2) A, b = 9.1926(1) A, c = 20.8006(1), beta =106.176(2) degrees, Z = 4]. In the solid state Mn(IV)-CN bond homolysis is thermally activated above 122 degrees C, according to differential scanning calorimetry measurements, leading to the reductive elimination of cyanogen. The [Mn(II)(CN)(4)](2-) ion has a dynamic solution behavior, as evidenced by its concentration-dependent electronic and electron paramagnetic spectra, that can be attributed to aggregation of the coordinatively and electronically unsaturated (four-coordinate, 13-electron) metal center. Due to dynamics and lability of [Mn(II)(CN)(4)](2-) in solution, its reaction with divalent first-row transition metal cations leads to the formation of lattice compounds with both tetrahedral and square planar local coordination geometries of the metal ions and multiple structural and cyano-linkage isomers. alpha-Mn(II)[Mn(II)(CN)(4)] has an interpenetrating sphalerite- or diamond-like network structure with a unit cell parameter of a = 6.123 A (P43m space group) while a beta-phase of this material has a noninterpenetrating disordered lattice containing tetrahedral [Mn(II)(CN)(4)](2-). Linkage isomerization or cyanide abstraction during formation results in alpha-Mn(II)[Co(II)(CN)(4)] and Mn(II)[Ni(II)(CN)(4)] lattice compounds, both containing square planar tetracyanometalate centers. alpha-Mn(II)[Co(II)(CN)(4)] is irreversibly transformed to its beta-phase in the solid state by heating to 135 degrees C, which causes a geometric isomerization of [Co(II)(CN)(4)](2)(-) from square planar (nu(CN) = 2114 cm(-1), S = (1)/(2)) to tetrahedral (nu(CN) = 2158 cm(-1), S = (3)/(2)) as evidenced by infrared and magnetic susceptibility measurements. Mn(II)[Ni(II)(CN)(4)] is the only phase formed with Ni(II) due to the high thermodynamic stability of square planar [Ni(II)(CN)(4)](2)(-).     

Platinum(II)-mediated coupling reactions of acetonitrile with the exocyclic nitrogen of 9-methyladenine and 1-methylcytosine. Synthesis, NMR characterization, and X-ray structures of new azametallacycle complexes

The hydroxo complex cis-[L2Pt(mu-OH)]2(NO3)2, (L = PMePh2, 1a), in CH3CN solution, deprotonates the NH2 group of 9-methyladenine (9-MeAd) to give the cyclic trinuclear species cis-[L2Pt[9-MeAd(-H)]]3(NO3)3, (L = PMePh2, 2a), in which the nucleobase binds the metal centers through the N(1), N(6) atoms. In solution at room temperature, 2a slowly reacts with the solvent to form quantitatively the mononuclear azametallacycle cis-[L2PtNH=C(Me)[9-MeAd(-2H)]]NO3 (L = PMePh2, 3a), containing as anionic ligand the deprotonated form of molecule N-(9-methyl-1,9-dihydro-purin-6-ylidene)-acetamidine. In the same experimental conditions, the hydroxo complex with PPh3 (1b) forms immediately the insertion product 3b. Single-crystal X-ray analyses of 3a and 3b show the coordination of the platinum cation at the N(1) site of the purine moiety and to the N atom of the inserted acetonitrile, whereas the exocyclic amino nitrogen binds the carbon atom of the same CN group. The resulting six-membered ring is slightly distorted from planarity, with carbon-nitrogen bond distances for the inserted nitrile typical of a double bond [C(3)-N(2) = 1.292(7) Angstroms in 3a and 1.279(11) Angstroms in 3b], while the remaining CN bonds of the metallocycle are in the range of 1.335(8)-1.397(10) Angstroms. A detailed multinuclear 1H, 31P, 13C, and 15N NMR study shows that the nitrogen atom of the inserted acetonitrile molecule binds a proton suggesting for 3a,b an imino structure in solution. In DMSO and chlorinated solvents, 3a slowly releases the nitrile reforming the trinuclear species 2a, whereas 3b forms the mononuclear derivative cis-[L2Pt[9-MeAd(-H)]]NO3 (L = PPh3, 4b), in which the adeninate ion chelates the metal center through the N(6) and N(7) atoms. Complex 4b is quantitatively obtained when 1b reacts with 9-MeAd in DMSO and can be easily isolated if the reaction is carried out in CH(2)Cl(2). In CH(3)CN solution, at room temperature, 4b slowly converts into 3b indicating that the insertion of acetonitrile is a reversible process. A similar metal-mediated coupling reaction occurs when 1a,b react with 1-methylcytosine (1-MeCy) in CH(3)CN. The resulting complexes, cis-[L(2)PtNH=C(Me)[1-MeCy(-2H)]]NO3, (L = PMePh2, 5a and PPh3, 5b), contain the deprotonated form of the ligand N-(1-methyl-2-oxo-2,3-dihydro-1H-pyrimidin-4-ylidene)-acetamidine. The X-ray analysis of 5a shows the coordination of the metal at the N(3) site of the pyrimidine cycle and to the nitrogen atom of the acetonitrile, with features of the six-membered metallocycle only slightly different from those found in 3a and 3b. In CD3CN/CH3(13)CN solution complexes 5a,b undergo exchange of the inserted nitrile, while in DMSO or chlorinated solvents they irreversibly release CH3CN to form species not yet fully characterized. No insertion of CH3CN occurs when the hydroxo complexes are stabilized by PMe3 and PMe2Ph.     

Dinuclear cyano-bridged CoIII-FeII complexes as precursors for molecular mixed-valence complexes of higher nuclearity

The preparation and characterization of a series of trinuclear mixed-valence cyano-bridged Co(III)-Fe(II)-Co(III) compounds derived from known dinuclear [[L(n)Co(III)(mu-NC)]Fe(II)(CN)(5)](-) complexes (L(n)() = N(5) or N(3)S(2) n-membered pendant amine macrocycle) are presented. All of the new trinuclear complexes were fully characterized spectroscopically (UV-vis, IR, and (13)C NMR). Complexes exhibiting a trans and cis arrangement of the Co-Fe-Co units around the [Fe(CN)(6)](4-) center are described (i.e., cis/trans-[{L(n)Co(III)(mu-NC)](2)Fe(II)(CN)(4)](2+)), and some of their structures are determined by X-ray crystallography. Electrochemical experiments revealed an expected anodic shift of the Fe(III/II) redox potential upon addition of a tripositively charged [Co(III)L(n)] moiety. The Co(III/II) redox potentials do not change greatly from the di- to the trinuclear complex, but rather behave in a fully independent and noncooperative way. In this respect, the energies and extinction coefficients of the MMCT bands agree with the formal existence of two mixed-valence Fe(II)-CN-Co(III) units per molecule. Solvatochromic experiments also indicated that the MMCT band of these compounds behaves as expected for a class II mixed-valence complex. Nevertheless, its extinction coefficient is dramatically increased upon increasing the solvent donor number.     

两个基于MnⅢ席夫碱氰基桥联化合物的合成、结构和磁性

本文利用MnⅢ席夫碱配合物作为前驱体,与含有氰根桥联配体的构筑基块K3[CoⅢ(CN)6]或Na[N(CN)2]反应合成了2个新的化合物[MnⅢ6(Salen)6(H2O)6.CoⅢ(CN)6][CoⅢ(CN)6].6H2O(1)和[MnⅢ(5-Br)Salen.N(CN)2].H2O(2),其中Salen为二-邻苯甲醛乙二胺。利用红外光谱、元素分析和X-射线单晶衍射分析对其结构进行了表征并测试了其磁学性质。结构分析表明化合物1由1个七核阳离子簇[Mn6Co]3+和一个平衡阴离子[Co(CN)6]3-组成的离子对化合物。而化合物2则为由MnⅢ组成的一维中性链结构,[N(CN)2]-利用叠氮桥联方式和金属离子配位。磁性研究表明,化合物1中[Co(CN)6]3-几乎不传递磁耦合作用,所以是一个顺磁体,但MnⅢ自身的零场分裂导致低χMT在低温时随温度下降而减小,而2则表现出弱的链内反铁磁性耦合作用。对比化合物1和2的磁性得知共轭体系[N(CN)2]-比同样是五原子配体[Co(CN)6]3-传递较强磁耦合作用。     

Similarities and differences between cobalamins and cobaloximes. Accurate structural determination of methylcobalamin and of LiCl- and KCl-containing cyanocobalamins by synchrotron radiation

The accurate crystal structure determinations of MeCbl (1), CNCbl.2LiCl (2), and CNCbl.KCl (3), based on synchrotron diffraction data collected at 100 K and using high-quality single crystals, are reported. Refinements gave R1 indices of 0.0834 (1), 0.0434 (2), and 0.0773 (3). The influence of the water of crystallization and ion content on the crystal packing of these and other cobalamins (XCbl) is discussed, and a relationship between the crystal packing and the corrin side chain conformations is presented. An analysis of the bond lengths within the corrin moiety, based on 13 accurate structures with several X groups, shows that the trend of the C-C and C-N distances can be interpreted in terms of electronic and steric factors. The variation in structural, NMR and IR spectroscopic, and electrochemical properties are compared with those of cobaloximes, the B12 model, when X is varied. This comparison indicates that the pi-back-donation from metal to the CN axial ligand and the transmission of the trans influence of the X ligand are more effective in cobalamins than in cobaloximes. These findings are consistent with a significantly greater availability of electron charge on Co in cobalamins, and, hence, a semiquantitative evaluation of the electronic difference between the cobalt centers in the two systems is allowed.     

The pressure tunning Raman and IR spectral studies on the multinuclear metal carbyne complexes

The Raman and infrared (IR) spectra of four tungsten metal carbyne complexes I, II, IV and V [Cl(CO)2(L)W[triple bond]CC6H4[triple bond](C[triple bond]CC6H4)n[triple bond]N[triple bond]C[triple bond]]2M (L = TMEDA, n = 0, M = PdI2 or ReCl(CO)3; L = DPPE, n = 1, M = PdI2 or ReCl(CO)3) were studied at high external pressure. Their pressure-induced phase transitions were observed near 20kbar (complexes I), 15 kbar (complexes II), 25 kbar (complex IV) and 30 kbar (complex V). The pressure-induced phase transition likely is first order in complex I and the pressure-induced phase transitions of complexes II, IV and V are mostly second order. The pressure sensitivities d nu/dp of nu(W[triple bond]C) are high in the low-pressure phase area and very low in the high-pressure phase area due to the pressure strengthening pi back-bonding from metal W to pi* orbital of C[triple bond]O in fragment Cl(CO)2(L)W[triple bond]C. The pressure strengthening metal pi back-bonding from metal Re or Pd to pi* orbital of C[triple bond]O or C[triple bond]N also happened to both of central metal centers of NCPd(I2)CN in complex I and NCReCl(CO)3CN in complex II.     

Synthesis and spectroscopic study of 2-butenedioic acid (Z)-monophenyl ester and its ethereal oxygen coordinated complexes with Th(IV) and Ce(IV)

2-Butenedioic acid (Z)-monophenyl ester and its complexes with tetravalent thorium and cerium have been synthesized and characterized by means of elemental analysis, TG-DTA, IR, ¹H NMR and ¹³C NMR spectra. Chemical analysis and TG-DTA analysis indicated that the complexes possess the formula: ML₂(OH)₂ (M?=?Th or Ce; L?=?(Z)-monophenyl ester-2-butenedioate ion). The spectroscopic studies showed that besides the bidentate carboxylate bonded to the central tetravalent metal ions, the ethereal oxygen also coordinated. This was indicated by a higher wave number shift of ν_C=O in the complexes than that of free ligand and its sodium salt, and a remarkable upfield chemical shift of carbon atom (C-8) in the p-position of ethereal oxygen substituted phenyl.     

Hydrogenation of 2,4-hexadienoic acid methyl ester

Hydrogenation of 2,4-hexadienoic acid methyl ester on supported metal catalysts (Pd/C, Pt/C, Rh/C and Ru/C) has been investigated. Methyl esters of 2-hexenoic and 3-hexenoic acids were formed and further hydrogenated to the methyl ester of hexanoic acid. Palladium was found to be the most active and selective catalyst for this reaction owing to the formation of intermediates.     

Structural, vibrational and quantum chemical investigations on 5-chloro-2-hydroxybenzamide and 5-chloro-2-hydroxybenzoic acid

The Fourier transform infrared (FTIR) and FT-Raman spectra of 5-chloro-2-hydroxybenzamide (5CBA) and 5-chloro-2-hydroxybenzoic acid (5C2HBA) have been recorded in the range 4000-400 and 4000-100 cm(-1), respectively. The complete vibrational fundamental modes of the compounds were assigned and analysed using the observed FTIR and FT-Raman data. The vibrational frequencies determined experimentally were compared with the theoretical wavenumbers calculated from ab initio HF and DFT-B3LYP gradient methods employing 6-31G** and 6-311++G** basis sets. The effect of halogen, hydroxyl groups and hydrogen bonding on the characteristic frequencies of the -COOH and -CONH2 group frequencies have been investigated. In 5CBA and 5C2HBA intramolecular hydrogen bond between a hydroxyl group and CO group makes a six membered ring, which causes the O?H interaction onto the resonance of the benzene ring. Comparison of the positions of the ν(OH) bands shows the ν(OH) band of 5CBA is located at considerably higher frequency which confirms a weaker hydrogen bond than in 5C2HBA.     

Oxidation of mixed-valence Co(III)/Fe(II) complexes reversed at high pH: a kinetico-mechanistic study of water oxidation

The outer-sphere oxidation of Fe(II) in the mixed-valence complex trans-[L(14S)Co(III)NCFe(II)(CN)(6)](-), being L(14S) an N(3)S(2) macrocylic donor set on the cobalt(III) center, has been studied. The comparison with the known processes of N(5) macrocycle complexes has been carried out in view of the important differences occurring on the redox potential of the cobalt center. The results indicate that the outer-sphere oxidation reactions with S(2)O(8)(2-) and [Co(ox)(3)](3-) involve a great amount of solvent-assisted hydrogen bonding that, as a consequence from the change from two amines to sulfur donors, are more restricted. This is shown by the more positive values found for DeltaS(#) and DeltaV(#). The X-ray structure of the oxidized complex has been determined, and it is clearly indicative of the above-mentioned solvent-assisted hydrogen bonding between nitrogen and cyanide donors on the cobalt and iron centers, respectively. trans-[L(14S)Co(III)NCFe(III)(CN)(6)], as well as the analogous N(5) systems trans-[L(14)Co(III)NCFe(III)(CN)(6)], trans-[L(15)Co(III)NCFe(III)(CN)(6)], and cis-[L(13)Co(III)NCFe(III)(CN)(6)], oxidize water to hydrogen peroxide at pH > 10 with a rather simple stoichiometry, i.e., [L(n)()Co(III)NCFe(III)(CN)(5)] + OH(-) --> [L(n)()Co(III)NCFe(II)(CN)(5)](-) + (1)/(2)H(2)O(2). In this way, the reversibility of the iron oxidation process is achieved. The determination of kinetic and thermal and pressure activation parameters for this water to hydrogen peroxide oxidation leads to the kinetic determination of a cyanide based OH(-) adduct of the complex. A second-order dependence on the base concentration is associated with deprotonation of this adduct to produce the final inner-sphere reduction process. The activation enthalpies are found to be extremely low (15 to 35 kJ mol(-1)) and responsible for the very fast reaction observed. The values of DeltaS(#) and DeltaV(#) (-76 to -113 J K(-1) mol(-1) and -5.5 to -8.9 cm(3) mol(-1), respectively) indicate a highly organized but not very compressed transition state in agreement with the inner-sphere one-electron transfer from O(2-) to Fe(III).