Organometallic cluster complexes containing ynamine ligands

A comprehensive review of the chemistry of metal carbonyl cluster complexes containing ynamine ligands including syntheses, structures, bonding, and reactivity is presented.     

A novel method for the synthesis of dichloroalkenes

A novel convenient method for the synthesis of dichloroalkenes was developed. The method involves catalytic olefination of hydrazones of aliphatic carbonyl compounds with bromo(trichloro)methane.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2538–2540, November, 2004.     

CO~2(CO)~8/吡啶络合催化苯乙烯氢羧化反应的研究

在苯乙烯氢羧化反应(Hydrocarboxylation)中,Co_2(CO)_8的催化活性很低,吡啶的加入可显著提高催化活性,Co_2(CO)_8与吡啶的配比不同时,对反应活性、收率和正、异构产物的比例均有影响,而且与反应温度有关。此外,还观察了各种吡啶衍生物对氢羧化反应的影响。     

碱改性γ-Al_2O_3催化剂上羰基硫的低温水解反应 Ⅰ.催化剂活性及补偿效应

以γ-Al_2O_3为载体,用浸渍法负载碱金属和碱土金属氧化物制备了一系列羰基硫水解催化剂。采用微反-色谱联用装置考察了45—100℃低温区内的活性变化规律。结果表明,催化剂活性与金属氧化物组分及含量有着密切关系。在考察各催化剂在不同温度下水解反应速度常数(K)的变化中,发现指前因子(A)与活化能(E)之间存在着补偿效应,活化能增大时指前因子也随之增大。补偿效应参数(K_0)和能量分布指前因子(1/b)均与负载的金属离子半径(d_m)有关。求得了各催化剂的等动力学温度(T),讨论了羰基硫水解反应中存在补偿效应的原因。     

羰基铁催化黄樟油素、丁香酚异构化反应的研究——Ⅲ.反应机理的研究

本文进一步研究了羰基铁络合物光催化黄樟油素(1)和丁香酚(2)异构化反应的机理。催化剂Fe(CO)_4(butadiene)和Fe(CO)_3(butadiene)对1和2具有几乎相同的活化能以及动力学参数(m,n),这说明反应可能经过同一类型的过渡态。在320～610 nm间进行光异构化反应时,只要光的波长能分解催化剂,则反应就能进行,这说明反应的关键是配位不饱和羰基铁与烯烃络合物的生成。     

含偶磷氮烷配体的三核钌羰基簇合物的合成和晶体结构

用Ru₃(CO)₁₂与顺-2,4二(叔丁基胺基)-1,3,-二(叔丁基)-1,3,2,4-环偶磷氮烷cis-[P(NHBu^t)NBu^t]₂反应,得到两个新的含偶磷氮环的三核钌羰基簇合物:Ru₃(CO)₁₁[{P(NHBu^t)NBu^t}₂] Ⅰ和Ru₃(CO)₁₁[P(NHBu^t)(NBu^t)₂P(O)H] Ⅱ。对它们进行了元素分析,IR和¹H NMR谱表征,并用X-ray单晶衍射法测定了晶体结构。Ⅰ:正交晶系,Pna2(1)空间群,a=2.7574(9) nm,b=0.8981(3) nm,c=1.5272(5) nm, V=3.782(2) nm³,D_c=1.686 g·cm^-3,Z=4;Ⅱ:三斜晶系,P1空间群,a=0.96384(19) nm,b=1.1705(2) nm,c=1.5589(3) nm,α=101.72(3) °,β=91.54(3) °,γ=108.20(3) °,V=1.6282(6)nm³,D_c=1.845g·cm^-3,Z=2;两个簇合物均为Ru₃(CO)₁₂的单取代衍生物,配位基环偶磷氮烷以单齿P原子配位在一个Ru原子的赤道位置上。Ⅱ中,偶磷氮环上未配位P(Ⅲ)被氧化成具有膦酰基结构(=P(O)H)的P(Ⅴ)。     

On the decrease in the ring π-current upon η6-coordination with a transition metal atom

A synthesis of [10]paracyclophane (Pc) and its organometallic complexes, Pc·Cr(CO)₃, [PcMn(CO)₃]⁺BF₄ ^–, (PcRuC₅Me₅)⁺·PF₆ ^–, (PcRhC₅Me₅)²⁺(BF₄ ^–)₂, and PcCo₄(CO)₉ has been carried out. The¹H NMR spectra of mononuclear complexes of neutral Cr and monocationic derivatives of Mn and Ru have been examined. ⁶-Coordination with a transition metal atom causes a decrease in the ring -current which is exhibited as a downfield displacement of the resonance signals from the protons of the --CH₂ groups in relation to those of free Pc. In the monocationic complexes the deshielding action of the positive charge is also added to this effect. In the¹H NMR spectrum of the cluster PcCo₄(CO)₉ the resonance signals from the --CH₂ protons are shifted upfield in relation to the Pc signals. Consequently, the concept of the ring -current decrease needs more detailed investigation for cluster systems.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1467–1470, August, 1993.     

应用硫酸铊作媒质的烯烃的电氧化反应

本文介绍使用硫酸亚铊为媒质,对环己烯、环庚烯、苯乙烯和1-十一烯进行电氧化反应、并研究生成羰基化合物的最佳反应条件。     

A novel binuclear copper complex incorporating a nalidixic acid derivative displaying a one‐dimensional coordination polymeric structure

The identification of the antibacterial action of nalidixic acid (nx) was central to the development of the quinolone antibacterial compounds. The ability of the nx naphthyridyl ring to interact with and inhibit some proteins has encouraged the investigation of similar structures in the search for more active compounds with less adverse effects. The possibility of structural modification by attachment of other biologically active moieties to the naphthyridyl ring of nx allowed the development of new active antimicrobial molecules. Hydrazone derivatives of nx can be synthesized easily based on the condensation of the hydrazide derivative of nx with the desired aldehyde or ketone. Only a few complexes with nx hydrazone derivatives have been described but for none were the crystal structures elucidated. The synthesis of a new one‐dimensional Cu^II coordination polymer, namely catena‐poly[[copper(II)‐di‐μ‐chlorido‐copper(II)‐{μ‐1‐ethyl‐N′‐[(1H‐imidazol‐4‐yl)methylidene]‐7‐methyl‐4‐oxo‐1,4‐dihydro‐1,8‐naphthyridine‐3‐carbohydrazidato}‐[dimethanolcopper(II)]‐{μ‐1‐ethyl‐N′‐[(1H‐imidazol‐3‐yl)methylidene]‐7‐methyl‐4‐oxo‐1,4‐dihydro‐1,8‐naphthyridine‐3‐carbohydrazidato}] dichloride methanol tetrasolvate], {[Cu₃(C₁₆H₁₅N₆O₂)₂Cl₂(CH₃OH)₂]Cl₂·4CH₃OH}_n, with the (1H‐imidazol‐4‐yl)methylidene carbohydrazide derivative of nalidixic acid (denoted h4imi), is presented and its structure is compared to the density functional theory (DFT) optimized structure of free h4imi. The title structure presents an octahedral Cu^II ion on an inversion centre alternating along a polymer chain with a square‐pyramidal Cu^II ion, with the two Cu^II centres bridged by two chloride ligands. Hydrogen bonds involving chloride counter‐ions and methanol solvent molecules mediate the three‐dimensional packing of the polymer. Comparison of the geometrical results from the structure analysis with those derived from a DFT study of the free ligand reveal the differences that arise upon coordination.