Resonance Raman studies of amaylose — iodine complexes

Resonance Raman measurements have been performed with solutions of iodine-complexed synthetic amyloses (DP 25–200), malto-oligomers (DP 3–18, and -cylodextrin. Interest was focused on the minimum chain length for helical complex formation and a possible preferred length for the polyiodine chain. Four fundamental vibrations are observed at 164, 112, 52 and 24 cm⁻¹. The 112 cm⁻¹ Raman line was shown to arise both from free I₃⁻ (enhanced at 363.8 nm excitation) and from bound iodine (relatively most intense at 457.9 nm excitation). The main signal of complexed iodine at 164 cm⁻¹is enhanced at an excitation wavelength close to the long wavelength absorption maximum. This signal is observed firt with malto-octaose and -cyclodextrin. The less intense signals at 52 and 24⁻¹ are only detected at DP 15 and higher. Raman spectra give no evidence for a preferred length of the polyiodine chain. Significantly identical Raman spectra are obtained when using different molar ratios of I₂/KI solution or I₂ solution initially free of I⁻ ions. The results are discussed in view of previous assignments of the Raman lines to I₂⁻, I₃⁻/I₂, and I₅⁻ subunits. Our findings are incompatible with I₃⁻ units as the only bound species. They are compatible with both I₃⁻/I₂ and I₃⁻ subunits under certain conditions. In the case of I₂ solution used for complexation we favour the polyiodine chain model proposed previously by Cramer^35,36. The I₃⁻ ions formed could function mainly as chain initiators, as has been suggested by Cesàro and Brant³⁰.     

Hydrozirconation/transmetalation of acetylenic stannanes. New 1,1-dimetallo reagents

Treatment of 1-tributylstannylalkynes with Cp₂Zr(H)CI affords olefinic intermediates substituted by both Bu₃Sn and Cp₂ZrCI groups on the terminal sp²-1ike carbon. These stereodefined reagents can be selectively transmetalated at zirconium to afford cuprates which deliver product vinyl stannanes in both substitution and Michael addition reactions.     

Reactivity, variable temperature solution H NMR studies and MO calculations of dimolybdenum allenylidene complexes of the type [(η-C5H5)2Mo2(CO)4(μ,η(4e)-C=C=CR1R2)]

The reactivity, towards nucleophiles and electrophiles, of dimolybdenum allenylidene complexes of the type [Cp₂Mo₂(CO)₄(μ,η²(4e)-C=C=CR1R2)] (Cp=η⁵-C₅H₅) has been investigated. The nucleophilic attacks occur at the C_γ carbon atom, while electrophiles affec the C atom. Variable temperature solution ¹H NMR studies show a dynamic behavior of these complexes consisting of an equilibrium between two enantiomers with a symmetrical [Cp₂Mo₂(CO)₄(μ-σ,σ(2e)-C=C=CR1R2)] transition state. Extended Hückel MO calculations have been carried out on the model [Cp₂Mo₂(CO)₄(μ,η²-C=C=CH₂]. The calculated charges of the allenylidene carbon atoms suggest that the electrophilic attacks are under charge control, while the nucleophilic attacks are rather under orbital control.     

The synthesis and reactivity of electrophilic iridium (III) complexes containing bis (diphenylphosphino) ethane

The complex Ir(CH₃) (CO) (CF₃SO₃)₂ (dppe) (1) has been synthesized from the reaction of Ir(CH₃)I₂(CO) (dppe) and silver triflate. Methane and IrH(CO) (CF₃SO₃)₂ (dppe) (2) are formed when a methylene chloride solution of 1 is placed under 760 torr dihydrogen. Conductivity studies indicate that methylene chloride solutions of complexes 1 and 2 are weak electrolytes and only partially ionized at concentrations above 1 mM. Complex 2 is an effective hydrogenation catalyst for ethylene and 1-hexene while acetone hydrogenation is inhibited by the formation of [IrH₂(HOCH(CH₃)₂) (CO) (dppe)] (OTf) (3). Linear dimerization and polymerization of styrene occurs via a carbocationic mechanism initiated by triflic acid elimination from 2. Treatment of an acetonitrile solution of Ir(CH₃)I₂(CO) (dppe) with silver hexafluorophosphate produces the solvent promoted carbonyl insertion product [Ir(C(O)CH₃) (NCCH₃)₃ (dppe)] [PF₆]₂ (7) which readily undergoes deinsertion in methylene chloride to form [Ir(CH₃) (CO) (NCCH₃)₂ (dppe)] [PF₆]₂ (8) and acetonitrile.     

N,N-expeditious dialkylation of cyclen (1,4,7,10-tetraazacyclododecane). An astonishing reactivity of cyclen tricarbonyl molybdenum and chromium complexes

After reaction with alkyl iodides and subsequent oxidative removal of the M(CO)₃ triprotection, molybdenum and chromium fac-LM(CO)₃ complexes of cyclen (L) unexpectedly lead to N¹,N⁷-dialkylated cyclen derivatives.     

The dicarbonylation of diiodomethane to malonate esters catalysed by triethylphosphine complexes of rhodium

Rhodium complexes, in the presence or absence of PEt₃, catalyse the carbonylation of CH₂I₂ to dialkylmalonates in the presence of alcohols (ROH, R=Me, Et, Pr¹, Bu) with side products from reactions in EtOH being CH₂(OEt)₂, EtI and traces of EtCO₂Et and EtOAc. The active species when using PEt₃ is shown to be [RhI(CO)(PEt₃)₂], formed via [Rh(OAc)(CO)(PEt₃)₂] from [Rh₂(OAc)₄ · 2MeOH] and PEt₃. Mechanistic studies show that the first step of the catalytic cycle is oxidative addition of CH₂I₂ to give [Rh(CH₂I)I₂(CO)(PEt₃)₂], but that insertion of CO into the Rh---CH₂I bond gives an iodoacyl complex which is unstable. The analogous [Rh(COCH₂X)X₂(CO)(PEt₃)₂], (X=Cl or Br) have been synthesised by oxidative addition of XCH₂COX to [RhX(CO)(PEt₃)₂] and fully characterised (by X-ray crystallography, for X=Cl). [Rh(COCH₂Br)Br₂(CO)(PEt₃)₂] has also been formed from reaction of [Rh(COCH₂Cl)Cl₂(CO)(PEt₃)₂] with excess NaBr. However, the analogous reaction with NaI does not give the iodoethanoyl complex, but rather [RhI₃(CO)(PEt₃)₂] and its decomposition products. It is proposed that [Rh(COCH₂I)I₂(CO)(PEt₃)₂] is unstable towards loss of I⁻ to form the ketene complex, [RhI₂(CH₂=C=O)(CO)(PEt₃)₂]I, which is transformed into [Rh(COCH₂CO₂Et)I₂(CO)(PEt₃)] by nucleophilic attack of ethanol at the central C atom, followed by CO insertion into the Rh---C bond. An analogue, [Rh(COCH₂CO₂Et)Cl₂(CO)(PEt₃)₂], has been isolated by oxidative addition of EtO₂CCH₂COCl across [RhCl(CO)(PEt₃)₂], and characterised both spectroscopically and crystallographically. In refluxing ethanol, [Rh(COCH₂CO₂Et)Cl₂(CO)(PEt₃)₂] produces diethylmalonate and [RhCl(CO)(PEt₃)₂], thus completing the catalytic cycle. Possible pathways of deactivation of the catalyst to give [RhI₃(CO)(PEt₃)₂] are discussed. One involves the reaction of ketene with ethanol to give EtOAc, whilst the others involve protonation of the Rh---Z bond in [RhZI₂(CO)(PEt₃)₂] (where Z =CH₂I, CH₂CO₂Et or H) by HI. The isolation of CH₂DCO₂Et, when carrying out the reaction in EtOD, is consistent with all of these deactivation pathways except protonation of [RhHI₂(CO)(PEt₃)₂].     

Toxicity of organotins towards cyanobacterial photosynthesis and nitrogen fixation

Abstract Inhibition of photosynthesis by a range of organotin compounds in Plectonema boryanum was concentration-dependent and decreased in the order tributyltin (Bu₃SnCl) > tripropyltin (Pr₃SnCl) ≥ dibutyltin (Bu₂SnCl₂) ≥ triphenyltin (Ph₃SnCl) > triethyltin (Et₃SnCl) > trimethyltin (Me₃SnCl) > monobutyltin (BuSnCl₃). IC₅₀ values were determined for the most toxic organotin species and varied from approximately 1.2 μM for Bu₃SnCl to approximately 13 μM for Ph₃SnCl. A similar order of inhibition of photosynthesis was observed in Anabaena cylindrica , although here IC₅₀ values were slightly lower (e.g. approximately 1 μM for Bu₃SnCl and 5 μM for Ph₃SnCl).Nitrogenase activity was generally more sensitive to inhibition by organotin compounds than photosynthesis in A. cylindrica and this was particularlyy evident for Bu₂SnCl₂; approximate IC₅₀ values for Bu₂SnCl₂ were 3 and 9 μM, as estimated by nitrogenase activity and photosynthesis, respectively. These results indicate that organotin compounds have the potential to inhibit cyanobacterial metabolism in aquatic systems.     

Synthesis and characterization of organomolybdenum and organotungsten halides containing the η-pentabenzylcyyclopentadienyl ligand η-Bz5C5M(CO)3X (M = Mo, W; X = Cl, Br, I). The X-ray molecular structure of η-Bz5C5Mo(CO)3I

An improved synthetic procedure for pentabenzylcyclopentadiene Bz₅C₅H was developed. Six new organomolybdenum and organotungsten halides η⁵-Bz₅C₅M(CO)₃X(M = Mo, W; X = Cl, Br, I) were syntesized through the reaction of η⁵-Bz₅C₅M(CO)₃Li (derived from Bz₅C₅H, n-BuLi and M(CO)₆) with PCl₃, PBr₃ or I₂ and characterized by elemental analysis, IR and ¹H NMR spectroscopy. The structure of η⁵-Bz₅C₅Mo(CO)₃I was determined by single-crystal X-ray diffraction techniques. It crystallized in the monoclinic space groupp P2/c with cell parameters a = 13.294(4), B = 15.147(4), C = 19.027(3) Å, β = 108.32(2)°, V = 3637(2) ų, Z = 4 and D_x = 1.50 g cm⁻³. The final R value was 0.035 for 4564 observed reflections.     

Hydroformylation of alkenes and alkynes using a heterobinuclear Rh---W catalyst

Hydroformylation reactions of a series of alkenes and alkynes have been carried out using the heteronuclear Rh---W catalyst, (CO)₄ hH(CO)(PPh₃) (1). The results of these reactions have been compared with corresponding reactions using [Rh(OAc)₂]₂ as catalyst. Catalysis of a reaction of styrene using 1 gave a very high yield of the branched chain aldehyde containing only a trace of the straight chain isomer. Reactions of the phosphinoalkene, Ph₂P(CH₂)₃CH=CH₂ (7) and the corresponding alkyne, Ph₂P(CH₂)₃CCH (11) gave similar products using either catalyst system with the alkryne reaction being significantly slower. Reaction of the alkenyl dithiane, H---CH₂CH=CH₂ (2), using the Rh---W catalyst (1) gave a higher ratio of linear to branched aldehydes (47 linear:53 branched) than the corresponding reaction using [Rh(OAc)₂]₂ (25 linear:75 branched). Reactions of vinyl acetate using 1 as catalyst gave a significant amount of linear aldehyde in contrast to reactions using [Rh(OAc)₂]₂ but reactions of allyl acetate gave similar products for both catalyst systems.     

Spectroscopic and electrical properties of the [W(C3Se5)3] anion complex (C3Se5 = 1,3-diselenole-2-selone-4,5-diselenolate) and the oxidized species

[NBuⁿ₄]₂[W(C₃Se₅)₃] (C₃Se₅²⁻ = 1,3-diselenole-2-selone-4,5- diselenolate(2−)) was prepared by the reaction of Na₂[C₃Se₅] with WCl₆ in ethanol, followed by addition of [NBuⁿ₄]Br. The cyclic voltammogram in dichloromethane exhibits two oxidation peaks at −0.04 and +0.03 V (versus SCE). The complex reacted with [Fe(C₅Me₅)₂][BF₄], iodine or [TTF]₃[BF₄]₂ (TTF^·+ = the tetrathiafulvalenium radical cation) in acetonitrile to afford the oxidized complexes [Fe(C₅Me₅)₂]_0.5[W(C₃Se₅)₃], [NBuⁿ₄]_0.1[W(C₃Se₅)₃] and [TTF]_0.5[W(C₃Se₅)₃], respectively. Current-controlled electrochemical oxidation of the complex in acetonitrile gave [NBuⁿ₄]_0.6[W(C₃Se₅)₃]. The oxidized complexes exhibit electrical conductivities of 4.7×10 ⁻⁵−1.5×10⁻³ S cm⁻¹ at room temperature measured for compacted pellets. Electronic absorption, IR and ESR spectra of these complexes are discussed.     

Transformations of molecular nitrogen into aromatic amines under the action of titanium compounds

The paper describes remarkable reactions of the direct synthesis of aromatic amines from molecular nitrogen. Two types of systems capable of inducing such reactions are considered in detail. The first type involves systems based on titanium compounds (Cp₂TiCl₂, Cp₂TiPh₂, CpTiCl₃, TiCl₄, Ti(OBu)₄) and excess aryllithium reagents (PhLi, p-, m- and o-MeC₆H₄Li, -C₁₀H₈Li, oPhC₆H₄Li) in ether. The second type is obtained by treating diaryltitanocenes Cp₂TiAr₂ (Ar = Ph, p- and m-MeC₆H₄) with metals of groups I and II (Li, Na, Mg) in ethereal media. In both cases the interaction with dinitrogen proceeds at room temperature and results in the formation of aromatic amines and ammonia after hydrolysis. The highest activity in amine production is displayed by the systems Cp₂TiCl₂ + PhLi in ether and Cp₂TiPh₂ + Li in THF. The mechanism of the reactions found is discussed.     

Model reactions of a carbonylation catalyst: phosphite induced migratory CO insertion in [MeIr(CO)2I3]

Carbonylation of the anionic iridium(III) methyl complex, [MeIr(CO)₂I₃]⁻ (1) is an important step in the new iridium-based process for acetic acid manufacture. A model study of the migratory insertion reactions of 1 with P-donor ligands is reported. Complex 1 reacts with phosphites to give neutral acetyl complexes, [Ir(COMe)(CO)I₂L₂] (L = P(OPh)₃ (2), P(OMe)₃ (3)). Complex 2 has been isolated and fully characterised from the reaction of Ph₄As[MeIr(CO)₂I₃] with AgBF₄ and P(OPh)₃; comparison of spectroscopic properties suggests an analogous formulation for 3. IR and ³¹P NMR spectroscopy indicate initial formation of unstable isomers of 2 which isomerise to the thermodynamic product with trans phosphite ligands. Kinetic measurements for the reactions of 1 with phosphites in CH₂Cl₂ show first order dependence on [1], only when the reactions are carried out in the presence of excess iodide. The rates exhibit a saturation dependence on [L] and are inhibited by iodide. The reactions are accelerated by addition of alcohols (e.g. 18× enhancement for L = P (OMe)₃ in 1:3 MeOH-CH₂Cl₂). A reaction mechanism is proposed which involves substitution of an iodide ligand by phosphite, prior to migratory CO insertion. The observed rate constants fit well to a rate law derived from this mechanism. Analysis of the kinetic data shows that k₁, the rate constant for iodide dissociation, is independent of L, but is increased by a factor of 18 on adding 25% MeOH to CH₂Cl₂. Activation parameters for the k₁ step are ΔH^≠ = 71 (±3) kJ mol⁻, ΔS^≠ = −81 (±9) J mol⁻¹ K⁻¹ in CH₂Cl₂ and ΔH^≠ = 60(±4) kJ mol⁻¹, ΔS^≠ = −93(± 12) J mol⁻¹ K⁻¹ in 1:3 MeOH-CH₂Cl₂. Solvent assistance of the iodide dissociation step gives the observed rate enhancement in protic solvents. The mechanism is similar to that proposed for the carbonylation of 1.     

Generation and spectroscopic characterization of new 18+δ electron complexes. Relationship between the stability of 18+δ electron organometallic complexes and their ligand reduction potentials

The relationship between the electrochemical reduction potential of a ligand and the ability of that ligand to form a kinetically inert 18+δ complex in a reaction with a 17-electron radical was investigated. (18+δ complexes are 19-electron adducts in which the unpaired electron is primarily located on a ligand orbital.) To probe the relationship, a series of 18+δ complexes was generated by irradiating the Cp′₂Mo₂(CO)₆, Cp₂Fe₂(CO)₄ and Co₂(CO)₈ dimers in the presence of a series of bidentate phosphorus ligands. (Irradiation of the dimers formed 17-electron metal radicals by photolysis of the metal-metal bonds.) These experiments showed that bidentate phosphorus ligands with reduction potentials more positive than −1 volt (versus SCE) formed long-lived 18+δ complexes (in THF or CH₂Cl₂ solutions at 23 °C), while ligands with potentials more negative than −1 V formed reactive 18+δ complexes. The inability to detect 18+δ complexes in the latter case is attributed to kinetic factors: the 18+δ complexes are powerful reductants and they readily initiate a chain disproportionation of the dimers by electron transfer. Analogous experiments with bidentate nitrogen ligands did not produce any detectable 18+δ complexes. In this case, the undetectability of the 18+δ complexes is probably thermodynamic in origin: the hard nitrogen ligands and soft metal centers form adducts that are unstable with respect to metal-nitrogen bond cleavage. 18+δ complexes are the subject of increasing interest, especially as models for their more reactive 19-electron-complex counterparts. These results provide some guidelines for the design of 18+δ complexes that can be synthesized, isolated and characterized for such studies.     

不同地下滴灌制度下黄瓜根际微生物活性及功能多样性

采用微生物培养、BIOLOG碳素利用法和土壤酶活性测定等方法,分析了日光温室不同地下灌溉制度下黄瓜根际土壤中微生物活性及功能多样性.结果表明: 根际土壤微生物生物量C、N含量、基础呼吸、代谢熵、AWCD值、Shannon指数和McIntosh指数随灌水量的增加呈先升高后下降的趋势;在0.8E_p(E_p为20 cm标准蒸发皿蒸发量)灌溉水平下,I2处理(灌水周期8 d)根际土壤微生物生物量C、N含量、基础呼吸、代谢熵、AWCD值、Shannon指数和McIntosh指数显著高于I₁处理(灌水周期4 d).0.8E_p处理下,细菌、放线菌、自生固氮菌数量及脲酶、磷酸酶、蔗糖酶、过氧化氢酶和多酚氧化酶活性显著高于其他2个灌水量处理（0.6E_p和1.0E_p）;I₂处理的细菌和自生固氮菌数量、脲酶、磷酸酶和蔗糖酶活性显著高于I₁处理,放线菌数量、过氧化氢酶和多酚氧化酶活性与I₁处理差异不显著,而真菌数量显著低于I₁处理.I 20.8E_p处理使黄瓜根际土壤中微生物代谢活性和微生物群落功能多样性升高,微生物区系得以改善,土壤酶活性提高,促进黄瓜生长.     

Lightinduced sulfur-dealkylation of phosphino-thioether nickel(0) complexes

The observation of homolytic S---CH₃ bond cleavage in (Ph₂P(o-C₆H₄)SCH₃)₂Ni⁰ under photochemical conditions has prompted further investigation of nickel(0) complexes and their stability. Tetradentate P₂S′₂ donor ligands (S′ = thioether type S donor) with aromatic rings incorporated into the P to S links, Ph₂P(o-C₆H₄)S(CH₂)₃S(o-C₆H₄)PPh₂ (arom-PSSP), or the S to S links, Ph₂P(CH₂)₂SCH₂(o-C₆H₄)CH₂S(CH₂)₂PPh₂ (PS-xy-SP), have been used to form four-coordinate, square planar nickel(II) complexes, [(arom-PSSP)Ni](BF₄)₂ (2) and [(PS-xy-SP)Ni](BF₄)₂ (3). The bidentate and tetradentate ligands, Ph₂P(o-C₆H₄)SCH₂CH₃ (arom-PSEt) and Ph₂P(CH₂)₂S(CH₂)₃S(CH₂)₂PPh₂ (PSSP), give similar complexes, [(arom-PSEt)₂Ni](BF₄)₂ (1) and [(PSSP)Ni](BF₄)₂ (4), respectively. Cyclic voltammograms of the Ni¹¹ complexes in CH₃CN show two reversible redox events assigned to and . The one-electron reduction product produced by stoichiometric amounts of Cp₂Co can be characterized by EPR. At 100 K rhombic signals show hyperfine coupling to two phosphorus atoms. Complete bulk chemical reduction of complexes 1, 2, 3 and 4 with Na/Hg amalgam provided the corresponding nickel(0) complexes 1^R, 2^R, 3^R and 4^R which were isolated as red solutions or solids characterized by magnetic resonance properties and reaction products. Photolysis of these nickel(0) complexes leads to S-dealkylation to produce alkyl radicals and dithiolate nickel(II) complexes. Complex 3 crystallized in the monoclinic space group P_2t/c with a=20.740(5), B=9.879(3), C=17.801(4) åA, ß=92.59(2)°, V=3644(2) ų and Z=4; complex 4: P2₁/c with A=13.815(4), B=13.815(4), C=15.457(5) åA, V=3365.4(14) ų and Z=4.     

The synthesis and reactions of A-ring aromatic steroid complexes of manganese tricarbonyl

Treatment of the A-ring aromatic steroids estrone 3-methyl ether and β-estradiol 3, 17-dimethyl ether with Mn(CO)₅⁺BF₄⁻ in CH₂Cl₂ yields the corresponding [(steroid)Mn(CO)₃]BF₄ salts 1 and 2 as mixtures of and β isomers. The X-ray structure of [(estrone 3-methyl ether)Mn(CO)₃]BF₄ · CH₂Cl₂ (1) having the Mn(CO)₃ moiety on the side of the steroid is reported: space group P2₁ with a=10.3958(9), b=10.9020(6), c=12.6848(9) Å, β=111.857(6)°, Z=2, V=1334.3(2) ų, _calc=.481 cm⁻³, R=0.0508, and wR=0.0635. The molecule has the traditional ‘piano stool’ structure with a planar arene ring and linear Mn---C---O linkages. The nucleophiles NaBH₄ and LiCH₂C(O)CMe₃ add to [(β-estradiol 3,17-dimethyl ether)Mn(CO)₃]BF₄ (2) in high yield to give the corresponding - and β-cyclohexadienyl manganese tricarbonyl complexes (3). The nucleophiles add meta to the arene -OMe substituent and exo to the metal. The and β isomers of 3 were separated by fractional crystallization and the X-ray structure of the β isomer with an exo-CH₂C(O)CMe₃ substituent is reported (complex 4): space group P2₁2₁2₁ with a=7.5154(8), b=15.160(2), c=25.230(3) Å, Z=4, V=2874.4(5) ų, _calc=1.244 g cm⁻³, R=0.0529 and wR2=0.1176. The molecule 4 has a planar set of dienyl carbon atoms with the saturated C(1) carbon being 0.592 Å out of the plane away from the metal. The results suggest that the manganese-mediated functionalization of aromatic steroids is a viable synthetic procedure with a range of nucleophiles of varying strengths.     

Titanium-carbon functionalities on an oxo surface defined by a calix [4] arene moiety and its redox chemistry

Lithiation of [p-Bu^t-calix[4]-(OMe)₂(OH)₂] (1), followed by reaction with TiCl₃(thf)₃ or TiCl₄(thf)₂, led to the corresponding titanium-calix[4]arene complexes [p-Bu^t-calix[4]-(OMe)₂(O)₂]TiCl] (2) and [p-Bu^t-calix[4]-(OMe)₂(O)₂]TiCl₂] (3), respectively. Reaction of 1 with TiCl₄(thf)₂ results in demethylation of the calix[4]arene and the obtention of [p-Bu^t-calix[4]-(OMe)₂(O)₃]TiCl] (4), whose hydrolysis led to [p-Bu^t-calix[4]-(OMe)(OH)₃] (6). The preparation of 6 can be carried out as a one-pot synthesis. Both 2 and 4 undergo alkylation reactions using conventional procedures, thus forming surprisingly stable organometallic species, namely [p-Bu^t-calix[4]-(OMe)₂(O)₂Ti(R)] (R = Me (7); CH₂Ph (8), p-MeC₆H₄ (9) and [p-Bu^t-calix[4]-(OMe)(O)₃Ti(R)] (R = Me (10); CH₂Ph (11); p-MeC₆H₄ (12)). Complexes 7 and 9 undergo a thermal oxidative conversion into 10 and 12, occurring with the demethylation of one of the methoxy groups. A solid state structural property of 9 and 12 has been revealed by X-ray analysis showing a self-assembly of the monomeric units into a columnar polymer, where the p-tolyl substituent at the metal functions as a guest group for an adjacent titanium-calixarene. Reductive alkylation of 3 with Mg(CH₂Ph)₂ gave 8 instead of forming the corresponding dialkyl derivative. Two synthetic routes have been devised for the synthesis of the Ti(III)-Ti(III) dimer [p-Bu^t-calix[4]-(OMe)(O)₃Ti]₂] (13): the reduction of 4 and the reaction of TiCl₃(thf)₃ with the lithiated form of 6. A very strong antiferromagnetic coupling is responsible for the peculiar magnetic behavior of 13. The proposed structures have been supported by the X-ray analyses of 4, 9, 12 and 13.     

Regio- and stereoselective dimerization of 1-alkynes catalyzed by an Os(II) complex

The complex [(PP₃)OsH(N₂)]BPh₄ is a catalyst precursor for the regio- and stereoselective dimerization of HCCR (R=Ph, SiMe₃) to (Z)-1,4-disubstituted-but-3-en-l-ynes (PP₃=P(CH₂CH₂PPh₂)₃). In the presence of H₂O or C₂H₅OH, the catalytic reaction with HCCSiMe₃ selectively gives but-3-en-l-ynyl-trimethyisilane. A detailed study under different experimental conditions, the detection of some intermediates, and the use of isolated complexes in independent reactions, taken altogether, permit mechanistic conclusions which account for the observed products. A key-role is played by (vinylidene)σ-alkynyl complexes which transform into η³-butenynyl derivatives via intramolecular C---C bond formation. The Os(II) η³-butenynyl complexes are likely reagents in the rate determining step of the catalytic cycle, and produce free (Z)-1,4-disubstituted-but-3-en-l-ynes upon σ-bond metathesis reaction with HCCR. The 16-electron fragments [(PP₃)OsX]⁺ (X = H, Cl, CCR) are capable of promoting the 1-alkyne to vinylidene tautomerism. In particular, the (vinylidene)hydride [(PP₃)OsH{C=C(H)-SiMe₃}]BPh₄ has been isolated and properly characterized. Since the stoichiometric reaction of the latter compound with HCCSiMe₃ gives vinyltrimethylsilane, the formation of (vinylidene)hydride species is suggested to be an effective step, alternative to 1-alkyne insertion, in the reduction of 1-alkynes to alkenes assisted by hydrido metal complexes.     

Reactivity of {(Ph3P)Pt[μ-η-H---SiH(Ar)]}2 (Ar=2-isopropyl-6-methylphenyl) with phosphines. X-ray crystal structure of trans-{(dppe)Pt[μ-SiH(Ar)]}2

The dinuclear Pt---Si complex {(Ph₃P)Pt{μ-η²-H---SiH(IMP)]}₂ (trans-1a–cis-1b=3:1; IMP=2-isopropyl-6-methylphenyl) reacted with basic phosphines such as 1,2-bis(diphenylphosphino)ethane (dppe) and dimethylphenylphosphine (PMe₂Ph) to afford different dinuclear Pt---Si complexes with loss of H₂, {(P)₂Pt[μ-SiH(IMP)]}₂ [P=dppe, trans-2a (major), cis-2b (trace); PMe₂Ph, 3 (trans only)]. Complexes 2 and 3 were characterized by multinuclear NMR spectroscopy and X-ray crystallography (2a). In contrast, the reaction of 1a,b with the sterically demanding tricyclohexylphosphine (PCy₃) afforded {(Cy₃P)Pt{μ-η²-H---SiH(IMP)]}₂ (trans-4a–cis-4b 2:1) analogous to 1a,b where the central Pt₂Si₂(μ-H)₂ core remains intact but the PPh₃ ligands have been replaced by PCy₃. Complexes 4a and 4b was characterized by multinuclear NMR and IR spectroscopies.