含杂环卡宾铁羰基簇合物的合成和结构

Fe(CO)~12与杂环硫代酰胺对它们进行了元素分析、IR、^1H NMR和MS表征, 并测定了晶体和分子结构反应, 在生成Fe(CO)~9(u-S)~2的同时, 还得到SLH劈开后以杂环卡宾配位的新羰合铁簇。     

含硫磷桥基的两核铁羰基簇合物的合成和晶体结构

Fe3(CO)12与杂环二硫代次膦酸盐SP(C6H4OR)(S)N(C6H5)NC(Me)(R=Me,Et)反应,得到两个新的含硫磷桥基的双核铁羰基簇合物Fe2(CO)6[μ-η2-SC(Me)NN(C6H5)P(C6H4OMe)](Ⅰ)和Fe2(CO)6[μ-η2-SC(Me)NN(C6H5)P(C6H4OEt)](Ⅱ),以及簇合物Fe3(CO)9(μ3-S)2(已知).对它们进行了元素分析,IR,1HNMR和MS等谱学表征,并用X-ray衍射技术测定了(Ⅰ)的晶体结构.该晶体属单斜晶系,P2(1)/n空间群,晶胞参数a=11.192(2)A,b=14.272(3)A,c=16.281(3)A,β=108.22(3).,V=2470.2(8)A3,Z=4.两核簇合物中含有两个桥基Fe-S-Fe和Fe-P-Fe,而且-C(7)-N(2)-N(1)-链连结在S、P原子间,形成了两个六员螯环Fe(1)SCNNP和Fe(2)PNNCS,增强了簇合物的稳定性.     

若干新型结构和新的成键方式的金属羰基簇合物

本文介绍了几位作者所合成并用X射线单晶结构分析表征的五类新型Fe,Co,Ru羰基簇合物。讨论其成键方式与结构特点。并介绍某些具有双键的配位基以不同的断裂方式提供不同的分子片配位于原子簇骨架的情况。     

含烯烃配体的过渡金属卡宾配合物的研究V:新型异构化的环己二烯(二羰基)[乙氧基(芳基)卡宾]铁配合物的合成和结构

报导了用含环状共轭双烯配体的1,3-环己二烯三羰基铁(1)与芳基锂在低温下的反应,并用Et3OBF4烷基化,以观察环烯烃配体的反应活性及其对卡宾配合物异构化的影响.并研究不同烯烃配体和芳烃取代基对产物的影响.     

钴原子簇化合物研究Ⅴ.含硫脲桥基三钴硫羰基簇合物的合成和结构

本文通过Co~2(CO)~8与5个取代硫脲R^1NHC(S)NHR^2反应,制得了通式Co~3(CO)~7(μ~3-S)[μ-η^2-R^1NC(S)NHR^2]5个新簇合物.除用碳氢氮元素分析、IR、^1HNMR和MS表征它们的结构外,还用X光衍射法测得R^11=Ph,R^2=CH~2Ph簇合物的单晶结构.该簇合物属三斜晶系,PI空间群.晶胞参数如下:a=0.9116(1),b=1.2289(2),c=1.2518(2)nm,a=115.56(1),β=100.92(2),γ93.29(1)°;z=2,Ⅴ=1226.2×10^-5nm^3;D~c=1.75g.cm^-3;μ=22.099cm^-1,F(000)=646.结构分析表明,该分子中的Co^3S原子构成三角锥分子骨架,所有CO为钴原子的端羰配体,而PhNC(S)NHCH~2Ph以S原子和与苯基相连的N原子分别与两个钴原子配位,形成Co~2NCS五圆环结构.     

含杂环卡宾碳的铁羰基簇合物的结构化学研究Ⅱ.—Fe3（CO）8（：CNH（S）C（…

Ｆｅ３（ＣＯ）１２和取代２，４－二硫代乙内酰脲反应，得到新的取代物Ｆｅ３（ＣＯ）８＾－（：ＣＮＨＣ（Ｓ）Ｃ（ＣＨ３）２ＮＨ（μ３－Ｓ２），并进行了ＩＲ，＾１ＨＮＭＲ，ＭＳ表征，测定了它的分析和晶体结构，讨论了杂环卡宾碎片：ＣＮＨＣ（Ｓ）Ｃ（ＣＨ３）２ＮＨ的取代位置，它是通过卡宾碳原子与Ｆｅ配位。     

过渡金属卡宾配合物:VIII. 四羰基[乙氧基(芳基)卡宾]铁配合物的方便合成法

五羰基铁, Fe(CO)~5(1), 与芳基锂(ArLi)在乙醚中于低温下反应, 所生成的酰羰基锂中间体在水溶液中于0℃用 Et~3OBF~4烷基化, 制得六个标题配合物(co)~4Fec(OC~1H~5)Ar(Ar:C~6H~5, 2;o-CH~3C~6H~4,3;p-CH~3C~6H~4, 4;p-CH~3OC~6H~4,5;C~6Cl~5,6;p-CF~3C~6H~4,7). 当用p-CF~3C~6H~4Li作为亲核试剂与1 反应时, 除生成7外, 还获得副产物对三氟甲基苯丙酮,p-CF~3C~6H~4COC~2H~5(8)。     

含2,4—二硫代乙丙酰脲分子片卡宾铁羰基簇合物的合成和结构

Ｆｅ３（ＣＯ）１２与５个２，４－二硫代乙内酰脲ＳＣＮＨＣ（Ｒ１）（Ｒ２）Ｃ（Ｓ）ＮＨ应制得通式为Ｆｅ３（ＣＯ）８（μ３－Ｓ）２（Ｌ）含卡宾配体的５个新铁羰基簇合物（１～５）对其进行了元素分析，ＩＲ、ＨＮＭＲ和ＭＳ表征，并用Ｘ射线衍射法测定了簇合物３的晶体和分子结构，表明２，４－二硫代乙内酰脲分子片配位基：ＣＮＨＣ（ＣＨ３）２Ｃ（Ｓ）ＮＨ的卡宾碳具有ｓｐ＾２成键特征，其Ｃ－Ｆｅ键长０．１８９８ｎｍ，     

过渡金属卡宾配合物:VIII. 四羰基[乙氧基(芳基)卡宾]铁配合物的方便合成法

五羰基铁, Fe(CO)~5(1), 与芳基锂(ArLi)在乙醚中于低温下反应, 所生成的酰羰基锂中间体在水溶液中于0℃用 Et~3OBF~4烷基化, 制得六个标题配合物(co)~4Fec(OC~1H~5)Ar(Ar:C~6H~5, 2;o-CH~3C~6H~4,3;p-CH~3C~6H~4, 4;p-CH~3OC~6H~4,5;C~6Cl~5,6;p-CF~3C~6H~4,7). 当用p-CF~3C~6H~4Li作为亲核试剂与1 反应时, 除生成7外, 还获得副产物对三氟甲基苯丙酮,p-CF~3C~6H~4COC~2H~5(8)。     

含硫帽的三核和四核钌羰基簇合物的合成和结构表征

The reaction of Ru₃(CO)₁₂ with five-membered cyclic SP(S)(Fc)N(Ph)NC(Me) gave two novel trinuclear and tetranuclear ruthenium carbonyl clusters containing capping S atoms in Ru₃(CO)₈(μ₃-S)₂[P(Fc)N(Ph)NC(Me)S] 1 and Ru₄(CO)₇(μ-CO)₃(μ₄-S)₂[P(Fc)N(Ph)NC(Me)S] 2 (Fc=C₅H₅FeC₅H₄). During the reaction, the ligand precursor cleaved only in its P=S bond to give the fragments S and [P(Fc)N(Ph)NC(Me)S], and then coordinated to the ruthenium atoms to form the clusters as listed above. The clusters have been characterized by elementary analysis, IR, ¹H NMR and MS spectroscopy. The crystal structure of cluster 2 has been determined by X-ary diffraction techniques. The crystal belongs to monoclinic with space group P2₁/c. The unit cell parameters are as follows: a=1.18744(7) nm, b=1.36041(11) nm, c=2.20026(18) nm, β=104.126(3) °, V=3.4468(5) nm³, D_c=2.175 g·cm^-3, Z=4. In the molecule, the three bridging carbonyls and Ru4 are planar and with a pseudo-octahedral Ru₄S₂ skeleton. The terminal carbonyl of Ru1 was substituted by the cyclic ligand [P(Fc)N(Ph)NC(Me)S]. CCDC: 217076.     

Synthesis,reactivity and preliminary biological activity of iron(0) complexes with cyclopentadienone and amino‐appended N‐heterocyclic carbene ligands

Neutral and cationic cyclopentadienone (CpO) N‐heterocyclic carbene (NHC) bis‐carbonyl iron(0) complexes bearing, appended to the NHC ligand, either a terminal amino group on the lateral chain, [Fe(η⁴‐CpO)(CO)₂(κC‐NHC(CH₂)_nNH₂)] with n = 2 ( 2a ) and 3 ( 2b ), or a cationic NMe₃⁺ fragment, [Fe(η⁴‐CpO)(CO)₂(κC‐NHC(CH₂)₂NMe₃)](I) ( 3 ), were prepared and characterized in terms of their structure, stability and reactivity. The photochemical properties of 2a and 2b were examined both in organic solvents and in water, revealing the photoactivated release of one CO ligand followed by the formation of the chelated complex [Fe(η⁴‐CpO)(CO)(κ²C,N‐NHC(CH₂)₂NH₂)] ( 4 ), whose molecular structure was confirmed by single crystal X‐ray diffraction studies. This metallacyclization occurs only in the case of 2a , with the ethylene spacer between NHC ring and NH₂ group in the lateral chain, allowing the formation of a stable 6‐membered ring. On the other hand, 2b undergoes decomposition upon irradiation. The reactivity in aqueous solutions revealed the chemical speciation of the complexes at different pH and especially under physiological conditions (phosphate buffer solution at pH 7.4 and 37 °C). The lack of data on the biological properties of iron(0) complexes prompted us to preliminarily investigate their cytotoxicity against model cancer cells (AsPC‐1 and HPAF‐II), along with a determination of their lipophilicity.     

Synthesis of heterocyclic carbene ligands via 1,2,3-diheterocyclization of allenylidene complexes with dinucleophiles

Heterocyclic carbene complexes are accessible from π-donor-substituted allenylidene complexes, [(CO)₅CrCCC(NMe₂)Ph] (1) and [(CO)₅CrCCC(O-endo-Bornyl)OEt] (4), and various dinucleophiles by 1,2,3-diheterocyclization. The reaction of 1 with 1,2-dimethylhydrazine gives the 1,2-dimethylpyrazolylidene complex (2) in high yield in addition to small amounts of the α,β-unsaturated carbene complex [(CO)₅CrC(NMe₂)-C(H)C(NMe₂)Ph] (3). The analogous reaction of 4 with 1,2-dimethylhydrazine affords the 1,2-dimethylpyrazolylidene complex (5) and, via displacement of the C_γ-bound ethoxy substituent, the hydrazinoallenylidene complex [(CO)₅CrCCC(O-endo-Bornyl){NMe-N(H)Me}] (6). Treatment of 6 with catalytic amounts of acids induces cyclization to 5. On addition of 1,1-dimethylhydrazine to 1 the zwitterionic pyrazolium-5-ylidene complex (7) is formed. The reaction of 1 with 1,2-diaminocyclohexane affords a octahydro-benzo[1,4]diazepinylidene complex (10) and, via intermolecular substitution, a binuclear bisallenylidene complex (11). Thiazepinylidene complexes (12-14), containing 7-membered N/S-heterocyclic carbene ligands, are formed highly selectively in the reaction of 1 with 2-aminoethanethiol or related cysteine derivatives by a substitution/cyclization sequence. The analogous reaction of 1 with homocysteine methylester yields a thiazocanylidene complex (15). All new heterocyclic carbene ligands are strong donors exhibiting σ-donor/π-acceptor ratios similar to those of the known imidazolylidene complexes. On photolysis of 2 and 12 in the presence of triphenylphosphine, the corresponding cis-carbene tetracarbonyl triphenylphosphine complexes (16 and 17) are formed. The solid state structure of complexes 2, 7, 14, 15, and 16 is established by X-ray structural analysis.     

Novel quasi‐scorpionate ligand structures based on a bis‐N‐heterocyclic carbene chelate core: synthesis,complexation and catalysis

A series of novel quasi‐scorpionate CNC donor ligands, MeC(2‐C₅H₄N){CH₂(imidazole‐R)} (R = methyl, n‐butyl, n‐propenyl), in which a chelating bis(NHC) core is supplemented by a hemi‐labile pyridyl donor, were prepared. The coordination chemistry of these ligands was investigated with silver, palladium, rhodium and iridium. The single crystal X‐ray structures of [Rh(NC₂^Me)(COD)]Cl 8a and [Ir(NC₂^Pr)(COD)]Br 9b were determined. The catalytic potential of the rhodium and iridium complexes was assessed in the transfer hydrogenation of ketones; the iridium complexes, which show superior performance, form very effective and stable catalysts. Copyright © 2011 John Wiley & Sons, Ltd.     

含杂环卡宾碳的铁羰基簇合物的结构化学研究Ⅱ．—Fe_3(CO)_8[:CNHC(S)C(CH_3)_2NH]的合成和晶体结构

Ｆｅ３（ＣＯ）＿（１２）和取代２，４＿二硫代乙内酰脲反应，得到新的取代物Ｆｅ３（ＣＯ）＿８－［：ＣＮＨＣ（Ｓ）Ｃ（ＣＨ＿３）＿２ＮＨ］（μ＿３－Ｓ）＿２，并进行了ＩＲ、１￣ＨＮＭＲ、ＭＳ表征，测定了它的分子和晶体结构，讨论了杂环卡宾碎片：ＣＮＨＣ（Ｓ）Ｃ（ＣＨ＿３）＿２ＮＨ的取代位置，它是通过卡宾碳原子与Ｆｅ配位。     

(N‐heterocyclic carbene)PdCl(N‐heterocyclic carboxylate) complexes: Synthesis and catalytic activities towards arylation of benzoxazoles with aryl halides

A series of N‐heterocyclic carboxylate‐stabilized N‐heterocyclic carbene palladium complexes have been synthesized and fully characterized. The solid‐state structures indicate that each of the palladium centers is coordinated by an N‐heterocyclic carbene, a chloride and a bidentate N,O‐donor N‐heterocyclic carboxylate ligand. The catalytic performance of the complexes was screened and the results revealed that the complexes exhibit moderate to high catalytic activities for the direct C─H bond arylation of benzoxazoles with aryl bromides.     

Group 4 complexes bearing alkoxide functionalized N‐heterocyclic carbene ligands as catalysts in the polymerization of olefins

Novel octahedral zirconium complexes bearing alkoxide functionalized N‐heterocyclic carbene ligands have been synthesized and characterized. NMR analysis showed that more than one species was obtained during synthesis. The synthesized complexes were able to polymerize ethylene and propylene giving rise to a linear polyethylene with high M_w and polydispersity index often bimodal with molecular weight distribution (MDI) > 2, and highly isotactic polypropylene together with an atactic fraction. Density functional theory (DFT) studies on the complex stability indicate the possible species active during the polymerization reaction. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Platinum (II) N‐heterocyclic carbene complexes: Synthesis,characterization and cytotoxic properties

Platinum (II) complexes bearing N‐heterocyclic carbene (NHC) ligands have been widely used in catalytic chemistry, but there are very few reports of biological properties of this type of complexes. A series of [PtCl₂(NHC)(PEt₃)] complexes were synthesized. The structures of all compounds were characterized by ¹H‐NMR, ¹³C‐NMR, IR and elemental analysis techniques, which supported the proposed structures. The single crystal structures of complexes 1a and 1e were determined. The title complexes show slightly distorted square‐planar coordination around the platinum (II) metal center. The cytotoxic properties of the platinum (II)–NHC complexes have been assessed in various human cancer lines, including cisplatin‐sensitive and resistant cells. IC₅₀ values of these four complexes were determined by the MTS‐based assay on three human cell lines—brain (SHSY5Y), colon (HTC116) and liver (HEP3B). These complexes have been highlighted cancer therapeutic agent with unique structures and functions.     

Synthesis,characterization and catalytic activity in Suzuki–Miyaura coupling of palladacycle complexes with n‐butyl‐substituted N‐heterocyclic carbene ligands

A series of monomeric palladacycle complexes bearing n‐butyl‐substituted N‐heterocyclic carbenes, namely [Pd(NHC)X(dmba)] (dmba: dimethylbenzylamine and [Pd(NHC)X(ppy)]; NHC: 1‐n‐butyl‐3‐substituted benzylimidazol‐2‐ylidene; ppy: 2‐phenylpyridine), were prepared either by transmetallation from the corresponding silver carbene complexes or by the reaction of the corresponding acetate‐bridged palladacycle dimer with N‐heterocyclic carbene ligands in high yields. The palladium(II) complexes were characterized using elemental analyses, APCI‐MS, ¹H NMR and ¹³C NMR spectroscopies. These complexes are efficient in the Suzuki–Miyaura coupling reaction between phenylboronic acid and aryl bromides.     

Synthesis of three-component high nuclearity cluster complexes with ruthenium carbido carbonyl clusters as a building block

Treatment of AgNO₃ with the Rh-Ru and Cu-Ru hetero bimetallic clusters, [PPN][RhRu₅C(CO)₁₄(cod)] and [PPh₄]₂[CuRu₆C(CO)₁₆Cl], afforded novel three-component complexes having one silver-, and two silver-bridges between respective cluster units, [PPN]{Ag[RhRu₅C(CO)₁₄(cod)]₂} and [PPh₄]₂{Ag₂[CuRu₆C(CO)₁₆Cl]₂}, respectively. Reaction of the ruthenium-copper cluster [PPh₄]₂{Cu₄[Ru₆C(CO)₁₆]₂Cl₂} (6) with Pd₂(dba)₃ · CHCl₃ gave another three-component cluster [PPh₄]₂{Cu₄Pd₂[Ru₆C(CO)₁₆]₂Cl₂} by incorporation of two palladium atoms. However, a similar reaction of 6 with Pt(dba)₂ gave only a two-component cluster complex, [PPh₄]₂{Pt₂[Ru₆C(CO)₁₅]₂}, while the reaction of silver analog [PPN]₂{Ag₄[Ru₆C(CO)₁₆]₂Cl₂} with Pd₂(dba)₃ · CHCl₃ resulted in the formation of known ruthenium-palladium cluster [PPN]₂{Pd₄[Ru₆C(CO)₁₆]₂}. Treatment of 6 with [RhCl(CO)₂]₂ gave two two-component clusters, [PPh₄][RhRu₅C(CO)₁₆] and [PPh₄]₂{Cu₇[Ru₆C(CO)₁₅]₂Cl₃}. All the new mixed-metal high nuclearity clusters have been characterized by single crystal X-ray analyses.     

Synthesis of cationic allyl complexes from trinuclear carbonyl clusters of iron,ruthenium and osmium

Thermal and photochemical reactions of trinuclear carbonyls of Fe, Ru, Os with allyl alcohol in acidic meclium as well as their reactions with (CH₃)₃NO · 2H₂O with subsequent protonation have been studied. Cationic mononuclear allyltetra-carbonyl complexes of Fe, Ru, Os and a cationic Os cluster with π-allyl ligand, have been obtained.