芳基取代茚基钌羰基化合物的合成及晶体结构

配体C₉H₇R(R=Ph(1),4-tolyl(2),4-chlorophenyl(3),4-methoxyphenyl(1),2-thienyl(5))分别与Ru₃(CO)₁₂在甲苯或二甲苯中加热回流,得到了5个双核配合物[(η⁵-C₉H₆R)Ru(CO)]₂(μ-CO)₂(R=Ph(6),4-tolyl(7),4-chlorophenyl(8),4-methoxyphenyl(9),2-thienyl(10))。通过元素分析、红外光谱、核磁共振氢谱对配合物的结构进行了表征,并用X-射线单晶衍射法测定了配合物6,7和10的结构。     

烃基取代茚基钌羰基化合物的合成及晶体结构(英文)

配体C9H7R(R=CH2CH2CH3(1),CH(CH3)2(2),C5H9(3),CH2C6H5(4),CH2CH=CH2(5))分别与Ru3(CO)12在二甲苯或庚烷中加热回流,得到了6个双核配合物[(η5-C9H6R)Ru(CO)(μ-CO)]2(R=CH2CH2CH3(6),CH(CH3)2(7),C5H9(8),CH2C6H5(9),CH2CH=CH2(10))和[(η5-C9H6)(H3CH2C)CHCH(CH2CH3)(η5-C9H6)][Ru(CO)(μ-CO)]2(11)。通过元素分析、红外光谱、核磁共振氢谱对配合物的结构进行了表征,并用X-射线单晶衍射法测定了配合物6,9,10和11的结构。     

烃基取代茚基钌羰基化合物的合成及晶体结构

配体C₉H₇R(R=CH₂CH₂CH₃ (1),CH₂(CH₃)₂ (2),C₅H₉ (3),CH₂C₆H₅ (4),CH₂CH=CH₂ (5))分别与Ru₃(CO)12在二甲苯或庚烷中加热回流,得到了6个双核配合物[(η⁵-C₉H₆R)Ru(CO)(μ-CO)]₂(R=CH₂CH₂CH₃ (6),CH₂(CH₃)₂ (7),C₅H₈ (8),CH₂C₆H₅ (9),CH₂CH=CH₂ (10))和[(η⁵-C₉H₆)(H₃CH₂C)CHCH(CH₂CH₃)(η⁵-C₉H₆)] [Ru(CO)(μ-CO)]₂ (11).通过元素分析、红外光谱、核磁共振氢谱对配合物的结构进行了表征,并用X-射线单晶衍射法测定了配合物6,9,10和11的结构.     

芳基取代茚基钌羰基化合物的合成及晶体结构

配体C₉H₇R(R=Ph (1),4-tolyl (2),4-chlorophenyl (3),4-methoxyphenyl (4),2-thienyl (5))分别与Ru₃(CO)₁₂在甲苯或二甲苯中加热回流,得到了5个双核配合物[(η⁵-C₉H₆R)Ru(CO)]₂(μ-CO)₂(R=Ph (6),4-tolyl (7),4-chlorophenyl (8),4-methoxyphenyl (9),2-thienyl (10))。通过元素分析、红外光谱、核磁共振氢谱对配合物的结构进行了表征,并用X-射线单晶衍射法测定了配合物6,7和10的结构。     

Reactions of Ruthenium–Allenylidene Complexes Tethering a Cyclopropyl Group

Two cyclopropyl allenylidene complexes [Ru]=CCC(R)(C₃H₅) ([Ru]=[RuCp(PPh₃)₂], Cp=Cyclopentadienyl; R=thiophene ( 2a ) and R=Ph ( 2b )) are prepared from the reactions of [Ru]Cl with the corresponding 1‐cyclopropyl‐2‐propyn‐1‐ol in the presence of KPF₆. Thermal treatment, halide‐anion addition, and palladium‐catalyzed reactions of 2a and 2b all lead to a ring expansion of the cyclopropyl group, giving the vinylidene complexes 4a and 4b , respectively, each with a five‐membered ring. This ring expansion proceeds by C C bond formation between Cβ of the cumulative double bond and a methylene group of the cyclopropyl ring. In the reaction of 2a with pyrrole, consecutive formation of two C C bonds, one between C‐2 of pyrrole and Cγ of 2a and the other between C‐3 of pyrrole and Cα, results in the formation of 6a . The reaction proceeds by addition of pyrrole and 1,3‐proton shifts. The hydrogenation of 2a by NaBH₄ is carried out in different solvents. The cumulative double bonds are reduced regioselectively to give a mixture of 7a and 8a . Interestingly, use of different solvents leads to different ratios of 7a and 8a . Presence of a protic solvent like methanol in dichloromethane or chloroform solution increases the yield of 8a , thus revealing that both the rates of hydroboration and deboronation increase. The structures of two new complexes 4a and 6a have been firmly established by X‐ray diffraction analysis.     

Strained Ruthenium Complexes Bearing Tridentate Guanidine-Derived Ligands

The dimer [{(η⁶-p-cymene)RuCl}₂(μ-Cl)₂] (cymene=MeC₆H₄ⁱPr) reacts with N,N′-bis(p-tolyl)-N′′-(2-pyridinylmethyl)guanidine ( H₂L1 ) and N,N′-bis(p-tolyl)-N′′-(2-diphenylphosphanoethyl)guanidine ( H₂L2 ), in the presence of NaSbF₆, giving rise to chlorido compounds of formula [(η⁶-p-cymene)RuCl( H₂L )][SbF₆] ( H₂L = H₂L1 ( 1 ), H₂L2 ( 2 )) in which the guanidine ligand adopts a κ² chelate coordination mode. The related ligand (S)-N,N′-bis(p-tolyl)-N′′-(1-isopropyl, 2-diphenylphosphano ethyl)guanidine ( H₂L3 ) affords mixtures of the corresponding chlorido compound [(η⁶-p-cymene)RuCl( H₂L3 )][SbF₆] ( 3 ) together with the complexes [(η⁶-p-cymene)RuCl₂( H₃L3 )][SbF₆] ( 4 ) and [(η⁶-p-cymene)Ru(κ³N,N′,P- HL3 )][SbF₆] ( 10 ) which contain phosphano-guanidinium and phosphano-guanidinate ions acting as monodentate and tridentate ligand, respectively. Compounds 1 , 2 and mixture of 3 / 4 / 10 react with AgSbF₆ rendering the cationic aqua-complexes [(η⁶-p-cymene)Ru( H₂L )(OH₂)][SbF₆]₂ ( H₂L = H₂L1 ( 5 ), H₂L2 ( 6 ), H₂L3 ( 7 )). These aqua-complexes exhibit a temperature-dependent fluxional process in solution. Experimental NMR studies and DFT theoretical calculations on complex 6 suggest that the process involves the exchange between two rotamers around one of the C−N guanidine bonds. Treatment of 5 – 7 with NaHCO₃ renders the complexes [(η⁶-p-cymene)Ru(κ³N,N′,N′′- HL1 )][SbF₆] ( 8 ) and [(η⁶-p-cymene)Ru(κ³N,N′,P- HL )][SbF₆] ( HL = HL2 ( 9 ), HL3 ( 10 )), respectively, in which the HL ligand adopts a fac κ³ coordination mode. The new complexes have been characterized by analytical and spectroscopic means, including the determination of the crystal structures of the compounds 1 , 2 , 5 , 9 and 10 , by X-ray diffractometric methods.     

高分子稳定的钌纳米金属簇选择性催化氢化巴豆醛

以聚乙烯吡咯烷酮稳定的钌纳米金属簇(PVP-Ru)为催化剂,进行了巴豆醛的选择性催化氢化。结果表明,反应体系中水和氢氧化钠的引入,可提高催化活性,但降低了选择性。某些金属阳离子对PVP-Ru的修饰作用使选择性有所提高,但降低了催化活性。尤其是经Co2 修饰后,巴豆醇的最高产率为5.5%,而催化活性由150.4 mol巴豆醛/mol Ru.h降至96.7 mol巴豆醛/mol Ru.h。     

Iridium and Ruthenium Complexes Bearing Perylene Ligands

The present review summarizes the work carried out mostly in the last decade on iridium and ruthenium complexes bearing various perylene ligands, of particular interest for bioimaging, photodynamic therapy, and solar energy conversion. In these complexes, the absorption spectra and the electrochemical properties are those of the perylene subunit plus those of the metal moiety. In contrast, the emissions are completely changed with respect to perylenes considered alone. Thus, fully organic perylenes are characterized by a strong fluorescence in the visible region, lifetimes of a few nanoseconds, and luminescence quantum yields approaching 100%, whereas perylene Ir and Ru complexes usually do not emit; however, in few cases, weak phosphorescent emissions, with lifetimes in the range of microseconds and relatively low quantum yields, are reported. This is due to a strong interaction between the perylene core and the heavy metal center, taking place after the excitation. Nevertheless, an important advantage deriving from the presence of the heavy metal center is represented by the ability to generate large amounts of singlet oxygen, which plays a key role in photodynamic therapy.     

Water Oxidation by Ruthenium Complexes Incorporating Multifunctional Bipyridyl Diphosphonate Ligands

We describe herein the synthesis and characterization of ruthenium complexes with multifunctional bipyridyl diphosphonate ligands as well as initial water oxidation studies. In these complexes, the phosphonate groups provide redox‐potential leveling through charge compensation and σ donation to allow facile access to high oxidation states. These complexes display unique pH‐dependent electrochemistry associated with deprotonation of the phosphonic acid groups. The position of these groups allows them to shuttle protons in and out of the catalytic site and reduce activation barriers. A mechanism for water oxidation by these catalysts is proposed on the basis of experimental results and DFT calculations. The unprecedented attack of water at a neutral six‐coordinate [Ru^IV] center to yield an anionic seven‐coordinate [Ru^IV?OH]^? intermediate is one of the key steps of a single‐site mechanism in which all species are anionic or neutral. These complexes are among the fastest single‐site catalysts reported to date.     

Cyclisation of dienes using phosphorus-centred radicals to form organophosphorus adducts

Reaction of various dienes with phosphites or related phosphorus hydrides, under free radical cyclisation conditions, affords cyclic organophosphorus adducts. This quick, mild and technically clean approach affords 5- and 6-ring carbocycles and heterocycles in good to excellent yield.     

New Ruthenium Complexes Based on Tetradentate Bipyridine Ligands for Catalytic Hydrogenation of Esters

New bipyridinemethanamine‐containing tetradentate ligands and their corresponding ruthenium complexes have been synthesized. The synthesized complexes performed well in the hydrogenation of a variety of esters with high efficiency (TON up to 9700) giving alcohols in good yields.     

Photocytotoxic Activity of Ruthenium(II) Complexes with Phenanthroline-Hydrazone Ligands

This paper reports on the synthesis and characterization of two new polypyridyl-hydrazone Schiff bases, (E)-N′-(6-oxo-1,10-phenanthrolin-5(6H)-ylidene)thiophene-2-carbohydrazide (L¹) and (E)-N′-(6-oxo-1,10-phenanthrolin-5(6H)-ylidene)furan-2-carbohydrazide (L²), and their two Ru(II) complexes of the general formula [RuCl(DMSO)(phen)(Lⁿ)](PF6). Considering that hydrazides are a structural part of severa l drugs and metal complexes containing phenanthroline derivatives are known to interact with DNA and to exhibit antitumor activity, more potent anticancer agents can be obtained by covalently linking the thiophene acid hydrazide or the furoic acid hydrazide to a 1,10-phenanthroline moiety. These ligands and the Ru(II) complexes were characterized by elemental analyses, electronic, vibrational, ¹H NMR, and ESI-MS spectroscopies. Ru is bound to two different N-heterocyclic ligands. One chloride and one S-bonded DMSO in cis-configuration to each other complete the octahedral coordination sphere around the metal ion. The ligands are very effective in inhibiting cellular growth in a chronic myelogenous leukemia cell line, K562. Both complexes are able to interact with DNA and present moderate cytotoxic activity, but 5 min of UV-light exposure increases cytotoxicity by three times.     

含席夫碱桥联配体的双核金属钌配合物的合成及其性能研究

合成了3种双核钌配合物[Ru(bpy)2]2{[(PyCHN)-Ph-O-C6H4-]2R}(ClO4)4,bpy=2,2′-联吡啶,PyCHN=N-2-吡啶亚甲基,R=无(1),-C(CH3)2(2),-SO2(3)并进行了有关表征。电化学研究表明:配合物3的ΔE和Kc值最大,说明苯环和硫原子之间存在着较强的(p(π)-d)π相互作用,有助于获得较强的金属-金属相互作用。配合物1,2,3都有混合价,通过Hush方程可以得到Vab的值大概为320~420 cm-1。这些结果表明:Schiff碱作为桥配体对于调配金属-金属相互作用并将其作为分子导线起着特殊的作用。     

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)。     

Hydrogen Atom Transfer-Mediated Domino Cyclisation Reaction to Access (Spiro)Quinazolinones

A radical domino cyclisation reaction of N-cyanamide alkenes, mediated by hydrogen atom transfer (HAT) has been developed. This method, using PhSiH₃ and catalytic Fe(acac)₃, allows for the synthesis of challenging (spiro)quinazolinone scaffolds from simple, tractable (hetero)aryl carboxylic acid and cyanamide building blocks.     

Synthesis and Catalytic Water Oxidation Activities of Ruthenium Complexes Containing Neutral Ligands

Two dinuclear and one mononuclear ruthenium complexes containing neutral polypyridyl ligands have been synthesised as pre‐water oxidation catalysts and characterised by ¹H and ¹³C NMR spectroscopy and ESI‐MS. Their catalytic water oxidation properties in the presence of [Ce(NH₄)₂(NO₃)₆] (Ce^IV) as oxidant at pH 1.0 have been investigated. At low concentrations of Ce^IV (5 mM ), high turnover numbers of up to 4500 have been achieved. An ¹⁸O‐labelling experiment established that both O atoms in the evolved O₂ originate from water. Combined electrochemical study and electrospray ionisation mass spectrometric analysis suggest that ligand exchange between coordinated 4‐picoline and free water produces Ru aquo species as the real water oxidation catalysts.     

取代联吡啶钌配合物对末端炔烃的催化环三聚作用

RuCl3·3H2O分别与6,6’-二甲基-2,2’-联吡啶(dmbp)和2,2’-联吡啶-6,6’-二甲醛(bpda)反应生成[cisRu(L)2Cl2]Cl·2H2O(L=dmbp,bpda),进一步用CF3SO3Ag脱氯得到[cis-Ru(L)2(H2O)2](CF3SO3)3.研究了4种配合物对1-己炔、苯乙炔和丙炔酸乙酯的催化环三聚作用,发现脱氯后的含水配合物催化活性有显著提高;体系中有水存在时,丙炔酸乙酯环三聚具有很强的区域选择性.催化机理研究表明,该催化过程为催化[2+2+2]环加成反应.钌杂环庚三烯或7-钌杂双环[2.2.1]-2,5-庚二烯是关键中间体,联吡啶配体上的6-甲酰基取代基水合后通过与丙炔酸乙酯的羰基形成分子内氢键影响环三聚产物的区域选择性.     

Slow Inversion of Coordinated Thioether Groups in SNS-Type Ruthenium Pincer Complexes

The thioether-group-containing SNS-type pincer complex [({EtSCH₂CH₂}₂NH)RuCl(H)(PPh₃)] ( 2 ) exists in three different diastereomers ( 2 a – c ). The molecular structures obtained from single crystal X-Ray diffraction studies of all three isomers reveal a difference in the relative orientation of the respective EtS-groups, while other commonly observed diastereomers as the result of cis-/trans- or fac-/mer-isomerism are not observed. Chemical exchange between the three diastereomers 2 a – c was discovered by phase-sensitive ¹H and ³¹P NOESY NMR spectroscopy, and further quantified by line shape analysis of ¹H NMR spectra. The experimentally derived averaged Gibbs energies of activation for the interconversion of the isomers (65–70 kJ/mol) are in good agreement with the results obtained from DFT calculations, which suggest an inversion of the ligating sulfur atoms, although a dissociative pathway for the configurational inversion can be competitive.     

Nitrogen Photofixation over III-Nitride Nanowires Assisted by Ruthenium Clusters of Low Atomicity

In many heterogeneous catalysts, the interaction of supported metal species with a matrix can alter the electronic and morphological properties of the metal and manipulate its catalytic properties. III-nitride semiconductors have a unique ability to stabilize ultra-small ruthenium (Ru) clusters (ca. 0.8 nm) at a high loading density up to 5 wt %. n-Type III-nitride nanowires decorated with Ru sub-nanoclusters offer controlled surface charge properties and exhibit superior UV- and visible-light photocatalytic activity for ammonia synthesis at ambient temperature. A metal/semiconductor interfacial Schottky junction with a 0.94 eV barrier height can greatly facilitate photogenerated electron transfer from III-nitrides to Ru, rendering Ru an electron sink that promotes N≡N bond cleavage, and thereby achieving low-temperature ammonia synthesis.     

Azodicarboxylate-Mediated Peptide Cyclisation: Application to Disulfide Bond Formation in Solution and Solid Phase

Cyclic peptides are important molecules, playing key roles in protein architecture, as chemical probes, and increasingly as crucial structural elements of clinically-useful therapeutics. Herein we report methodology using azodicarboxylates as efficient reagents for the facile synthesis of cyclic peptides through a disulfide bridge. The utility of this approach in both solution and solid-phase, and compatibility with common amino acid side chain functionalities is demonstrated, resulting in cyclic peptides in good yield and purity. This approach has significant potential application for synthesis of molecules of biological or therapeutic significance.