Ansa‐Bridged Bis(benzene) Titanium Complexes

Taking advantage of an improved synthesis of [Ti(η⁶‐C₆H₆)₂], we report here the first examples of ansa‐bridged bis(benzene) titanium complexes. Deprotonation of [Ti(η⁶‐C₆H₆)₂] with nBuLi in the presence of N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine (pmdta) leads to the corresponding 1,1′‐dilithio salt [Ti(η⁶‐C₆H₅Li)₂] ? pmdta that enables the preparation of the first one‐ and two‐atom‐bridged complexes by simple salt metathesis. The ansa complexes were fully characterized (NMR spectroscopy, UV/Vis spectroscopy, elemental analysis, and X‐ray crystallography) and further studied electrochemically and computationally. Moreover, [Ti(η⁶‐C₆H₆)₂] is found to react with the Lewis base 1,3‐dimethylimidazole‐2‐ylidene (IMe) to give the bent sandwich complex [Ti(η⁶‐C₆H₆)₂(IMe)].     

Ansa‐Complexes of [Mn(η5‐C5H5)(η6‐C6H6)]: Preparation,Characterization, and Reactivity of [n]Manganoarenophanes (n=1, 2, 3)

We report the synthesis of [n]manganoarenophanes (n=1, 2) featuring boron, silicon, germanium, and tin as ansa‐bridging elements. Their preparation was achieved by salt‐elimination reactions of the dilithiated precursor [Mn(η⁵‐C₅H₄Li)(η⁶‐C₆H₅Li)]?pmdta (pmdta=N,N,N′,N′,N′′‐pentamethyldiethylenetriamine) with corresponding element dichlorides. Besides characterization by multinuclear NMR spectroscopy and elemental analysis, the identity of two single‐atom‐bridged derivatives, [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] and [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SiPh₂], could also be determined by X‐ray structural analysis. We investigated for the first time the reactivity of these ansa‐cyclopentadienyl–benzene manganese compounds. The reaction of the distannyl‐bridged complex [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)Sn₂tBu₄] with elemental sulfur was shown to proceed through the expected oxidative addition of the Sn?Sn bond to give a triatomic ansa‐bridge. The investigation of the ring‐opening polymerization (ROP) capability of [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] with [Pt(PEt₃)₃] showed that an unexpected, unselective insertion into the C_ipso?Sn bonds of [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] had occurred.     

Transition‐Metal π‐Ligation of a Tetrahalodiborane

The reaction of tetraiododiborane (B₂I₄) with trans‐[Pt(BI₂)I(PCy₃)₂] gives rise to the diplatinum(II) complex [{(Cy₃P)(I₂B)Pt}₂(μ₂:η³:η³‐B₂I₄)], which is supported by a bridging diboranyl dianion ligand [B₂I₄]^2?. This complex is the first transition‐metal complex of a diboranyl dianion, as well as the first example of intact coordination of a B₂X₄ (X=halide) unit of any type to a metal center.     

Determination of average degree of polymerisation and distribution of oligosaccharides in a partially acid-hydrolysed homopolysaccharide: a comparison of four experimental methods applied to mannuronan

The average degree of polymerisation (DP) and distribution of oligosaccharides in partially acid hydrolysed mannuronans were quantitatively evaluated by 1H NMR, electrospray ionisation mass spectrometry (ESI-MS), micellar electrokinetic capillary chromatography with UV detection (MEKC-UV), and high-pressure anion-exchange chromatography with pulsed amperometric detection (HPAEC-PAD). Our investigation shows that 1H NMR, MEKC-UV and, in particular, HPAEC-PAD can be used as quantitative tools to aid the investigation of polysaccharide structure, function and synthesis. For the latter two techniques, especially, this represents a significant new development as it enables calculation of the quantity of individual oligomers of nominal DP by direct analysis of a defined oligomer mixture. Appropriate statistical averages of number and weight distributions were also calculated and found to fit very well to predicted Kuhn distributions that assume random depolymerisation.     

Boryl‐Functionalized σ‐Alkynyl and Vinylidene Rhodium Complexes: Synthesis and Electronic Properties

The synthesis, reactivity, and properties of boryl‐functionalized σ‐alkynyl and vinylidene rhodium complexes such as trans‐[RhCl(?C?CHBMes₂)(PiPr₃)₂] and trans‐[Rh(C?CBMes₂)(IMe)(PiPr₃)₂] are reported. An equilibrium was found to exist between rhodium vinylidene complexes and the corresponding hydrido σ‐alkynyl complexes in solution. The complex trans‐[Rh(C?CBMes₂)(IMe)(PiPr₃)₂] (IMe=1,3‐dimethylimidazol‐2‐ylidene) was found to exhibit solvatochromism and can be quasireversibly oxidized and reduced electrochemically. Density functional calculations were performed to determine the reaction mechanism and to help rationalize the photophysical properties of trans‐[Rh(C?CBMes₂)(IMe)(PiPr₃)₂].     

The efficient and selective oxidation of alcohols with zeolite NaY-supported sodium ruthenate

Primary and internal alcohols are efficiently oxidised to their corresponding oxidation products at room temperature by a newly synthesized zeolite NaY-supported sodium ruthenate. Advantages of this system include simple catalyst removal and product isolation, in addition to easy recycling of this catalyst.     

Nucleophilic Aromatic Substitution at Benzene with Powerful Strontium Hydride and Alkyl Complexes

Key to the isolation of the first alkyl strontium complex was the synthesis of a strontium hydride complex that is stable towards ligand exchange reactions. This goal was achieved by using the super bulky β‐diketiminate ligand ^DIPePBDI (CH[C(Me)N‐DIPeP]₂, DIPeP=2,6‐diisopentylphenyl). Reaction of ^DIPePBDI‐H with Sr[N(SiMe₃)₂]₂ gave (^DIPePBDI)SrN(SiMe₃)₂, which was converted with PhSiH₃ into [(^DIPePBDI)SrH]₂. Dissolved in C₆D₆, the strontium hydride complex is stable up to 70 °C. At 60 °C, H–D isotope exchange gave full conversion into [(^DIPePBDI)SrD]₂ and C₆D₅H. Since H–D exchange with D₂ is facile, the strontium hydride complex served as a catalyst for the deuteration of C₆H₆ by D₂. Reaction of [(^DIPePBDI)SrH]₂ with ethylene gave [(^DIPePBDI)SrEt]₂. The high reactivity of this alkyl strontium complex is demonstrated by facile ethylene polymerization and nucleophilic aromatic substitution with C₆D₆, giving alkylated aromatic products and [(^DIPePBDI)SrD]₂.     

The Synthesis of B2(SIDip)2 and its Reactivity Between the Diboracumulenic and Diborynic Extremes

A new compound with the formula L‐B₂‐L wherein the stabilizing ligand (L) is 1,3‐bis[diisopropylphenyl]‐4,5‐dihydroimidazol‐2‐ylidene (SIDip) has been synthesized, isolated, and characterized. The π‐acidity of the SIDip ligand, intermediate between the relatively non‐acidic IDip (1,3‐bis[diisopropylphenyl]imidazol‐2‐ylidene) ligand and the much more highly acidic CAAC (1‐[2,6‐diisopropylphenyl]‐3,3,5,5‐tetramethylpyrrolidin‐2‐ylidene) ligand, gives rise to a compound with spectroscopic, electrochemical, and structural properties between those of L‐B₂‐L compounds stabilized by CAAC and IDip. Reactions of all three L‐B₂‐L compounds with CO demonstrate the differences caused by their respective ligands, as the π‐acidities of the CAAC and SIDip carbenes enabled the isolation of bis(boraketene) compounds (L(OC)B‐B(CO)L), which could not be isolated from reactions with B₂(IDip)₂. However, only B₂(IDip)₂ and B₂(SIDip)₂ could be converted into bicyclic bis(boralactone) compounds.     

低频室内声散射计算机模拟方法

近年来,声散射的模拟成为室内声场计算机模拟研究的重点。现有的方法一般是依据壁面性质(结构、粗糙度等),利用经验确定散射系数,并基于该系数来模拟室内散射声能的分布。这种方法在低频情况下的精度较差,主要原因是忽略了在低频声场中起重要作用的波动现象。为此,本文提出一种新的计算壁面散射的模型,该模型既可考虑壁面上产生的散射声能,又可计算因壁面边缘衍射而产生的散射声能。文中通过模拟和实测数据的对比,分析验证了该模型的有效性,并给出了表面散射系数的取值规则。