四核钴羰基簇合物的合成和晶体结构

用Co₂(CO)₈与有机杂环二硫代次膦酸盐SP(C₆H₄OR)(S)N(C₆H₅)NC(Me)(R=Me,Et)反应,得到两类4个含S,P桥基配体的四核钴羰基簇合物Co₄(CO)₁₀(μ₄-S)[μ₄-P(C₆H₄OR)](1:R=Me;3:R=Et)和Co₄(CO)₁₀(μ₃-S)[μ₂-P(C₆H₄OR)N(C₆H₅)NC(Me)](2:R=Me,4:R=Et).在反应中,前配体中的PS键以及C-S,P-S,P-N键劈开,产生的分子片与金属钴原子配位,组建成新的羰基钴簇.对这4个簇合物进行了元素分析,IR,¹HNMR和MS谱学表征,并测定了簇合物4的晶体结构,该晶体属单斜晶系,P2₁/c空间群,晶胞参数a=1.9065(4)nm,b=1.0081(2)nm,c=1.6663(3)nm,β=97.36(3)°,V=3.1704(11)nm₃,Z=4,D_c=1.743g/cm³.Co1Co3Co4呈三角形分布,其中Co-Co平均键长为0.251nm,而Co₂在该三角平面的一侧,Co2-Co3键为0.269nm.该簇合物分子骨架为三角钉型结构,每个Co原子的立体几何均为变形八面体,但配位环境各不相同.     

钴原子簇化合物研究(Ⅳ)——含桥基杂环硫代酰胺基和杂环卡宾的三核钴羰基硫簇合物的合成及表征

用Co₂(CO)₃和杂环硫代酰胺SCXCH₂CH₂NH(X=NH,S,O)反应,得到两类6个新的可能具有手征性的三核钴羰基硫簇合物Co₃(CO)₇(μ₃-S)(μ-SCXCH₂CH₂N)(Ⅰ)和Co₃(CO))₆(μ₃-S)(:CXCH₂CH₂NH)(μ-SCXCH₂N)(Ⅱ).Ⅰ和Ⅱ的分子骨架Co₃S为四面体结构,其中SCXCH₂CH₂NH是通过S、N与2个Co键合的3e桥基配体,而:CXCH₂CH₂NH为2e杂环卡宾配体,对6个簇合物进行了表征,并对反应条件做了初步研究。     

具有含磷、硫配体的二核和三核钌羰基簇合衍生物的合成及晶体结构

用Ru₃(CO)12与杂环二硫代次膦酸盐SP(C₆H₄OR)(S)N(C₆H₅)NC(Me)(R=Me,Et)反应,得到两类4个含磷、硫配体的二核和三核钌羰基簇合衍生物Ru₃(CO)₈(μ₃-S)₂[P(C₆H₄OR)N(C₆H₅)NC(Me)S](1;R=Me;3;R=Et)和Ru₂(CO)₆[μ-η₂-SC(Me)NN(C₆H₅)P(C₆H₄OR)](2;R=Me;4;R=Et).对它们进行了元素分析、IR、¹HNMR和MS谱学表征,并用X射线衍射技术测定了1和2的晶体结构.晶体1属三斜晶系,P1空间群,晶胞参数a=1.0755(2)nm,b=1.5760(2)nm,c=0.9078(1)nm,α=98.12(7)°,β=96.64(4)°,γ=79.67(5)°,V=1.4921(4)nm³,Z=2,R(wR)=0.0303(0.0615);该簇合物分子为开口三核钌簇,其簇骨架Ru₃(μ₃-S)₂为畸变四方锥构型;五元杂环上的P原子取代在Ru1原子的轴向配位位置上.晶体2属单斜晶系,P2(1)/n空间群,晶胞参数a=1.1243(4)nm,b=1.4105(5)nm,c=1.62945(7)nm,β=107.06(5)°,V=2.4702(2)nm³,Z=4,R(wR)=0.0248(0.0441);两核簇合物分子中含有2个六元螯环Ru1SCNNP和Ru2SCNNP,增强了簇合物的稳定性.     

一种新型结构的七核钴原子羰基簇合物的合成与结构研究

C₂H₅SPCl₂与Co₂(CO)₈反应的产物经柱层析分离得3条带,第一条为深棕色,经IR谱、¹HNMR、谱、元素分析、X光单晶结构分析,确定该带产物为七核钴原子簇CO₇(μ₇-S)(μ₄-PSC₂H₅)(μ-SC₂H₅)₂(μ-CO)₂(CO)₁₂,是八面体骨架Co₄PS和四面体骨架Co₃S结合的松散原子簇合物。     

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,制得了通式为Co_3(CO)_7(μ3-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、~1H NMR和MS表征它们的结构外,还用X光衍射法测得R~1=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,α=115.56(1),β=100.94(2),γ=93.39(1)°;Z=2;V=1226.2×10~(-3)nm~3;D_c=1.750g·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(8)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.     

具有磷、氯桥基的三核钌羰基簇合物的合成和晶体结构

The reaction of Ru₃(CO)₁₂ with P(NEt₂)₂Cl, yields two trinuclear ruthenium carbonyl clusters: HRu₃(CO)₉[ μ₃-η²-P(NEt₂)₂]₂ Ⅰ (known) and a novel Ru₃(CO)₇( μ-Cl)₂[ μ-P(NEt₂)₂]₂ Ⅱ. During the reaction, the ligand precursor was cleaved in its P-Cl bond to give the fragments Cl and P(NEt₂)₂, and then coordinated to the ruthenium atoms to form the clusters as listed above. The crystal structure of cluster Ⅱ has been determined by X-ray diffraction technique. The crystal belongs to monoclinic with space group P2₁/c. The unit cell parameters are as follows: a=1.287 9(6) nm, b=1.653 9(8) nm, c=1.643 6(8) nm, β=95.786(7)°, V=3.483(3) nm³, D_c=1.756 g·cm^-3, Z=4. The cluster has a closed triangle Ru₃ framework. Two Ru-Ru bonds are supported by μ-P(NEt₂)₂, the other one is connected by double Cl bridging. The valence electrons of the cluster are 50e. CCDC: 231979.     

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.     

簇合物SFeCO2（CO）9的合成方法研究

簇合物ＳＦｅＣｏ＿２（ＣＯ）＿９的合成方法研究赵转云，武和平，殷元骐（中国科学院兰州化学物理研究所兰州７３００００）ＳＦｅＣｏ＿２（ＣＯ）＿９是一四面体构型的潜手性簇合物，由此为前体，合成簇合物ＳＦｅＣｏＭ（ＣＯ）＿ｘ（Ｍ＝Ｃｒ，Ｍｏ，Ｗ，Ｒｈ，Ｒｕ...     

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)。     

Fe3(CO)12与P(NEt2)2Cl的反应--两核和三核铁羰基簇合衍生物的合成和晶体结构

Fe_3(CO)_(12)与配位基前体P(NEt_2)_2Cl反应,给出4个新的两核和三核铁羰基簇合衍生物:Fe_2(CO)_6(μ-Cl)[μ-P(NEt_2)_2](Ⅰ),Fe_2(CO)_6[μ-P(NEt_2)_2]_2(Ⅱ),Fe_3(CO)_9(μ-CO)(μ_3-PNEt_2)(Ⅲ)和Fe_3(CO)_9(μ_3-PNEt_2)[P(NEt_2)_3](Ⅳ)。在反应期间,配前体分子中的P-Cl和P-N键劈开,形成的分子片Cl、PNEt_2、P(NEt_2)_2和P(NEt_2)_3作为配体与铁羰合物重新组建成上述簇合物。利用X射线衍射法测定了它们的晶体结构。Ⅰ属三斜晶系,P1空间群,晶胞参数a=0.8745(6)nm,b=0.9601(7)nm,c=1.3996(10)nm,α=74.131(11)°,β=79.480(12)°,γ=69.727(12)°,V=1.0553(13)nm~3,D_c=1.543g·cm~(-3),Z=2,R=0.0443,wR=0.0831。Ⅱ属正交晶系,Pbcn空间群,晶胞参数a=1.0153(3)nm,b=1.7543(5)nm,c=1.6860(5)nm,V=3.0031(15)nm~3,D_c=1.394g·cm~(-3),Z=4,R=0.0519,wR=0.1035。Ⅲ属单斜晶系,P2_1/c空间群,晶胞参数a=1.0280(5)nm,b=1.2113(5)nm,c=1.9192(7)nm,β=93.560(7)°,V=2.1366(16)nm~3,D_c=1.712g·cm~(-3),Z=4。Ⅳ属单斜晶系,Cc空间群,晶胞参数a=1.5875(7)nm,b=1.0359(5)nm,C=2.1919(9)nm,β=101.266(8)°,V=3.535(3)nm~3,Dc=1.443g·cm~(-3),Z=4。Ⅰ和Ⅱ为两核铁簇,其簇骨架Fe_2PCl和Fe_2P_2呈蝶状。Ⅲ和Ⅳ     

(μ-FcC≡CH)Co2(CO)6簇合物羰基取代衍生物的合成和分子结构

The substituted reactions of (μ-FcC≡CH)Co₂(CO)₆ with PPh₃, AsPh₃ and dppm have been studied and three new substituted derivatives have been obtained. The compounds were characterized by elemental analysis, IR, ¹H NMR, MS and X-ray crystallography. They have the following formula: (μ-FcC≡CH)Co₂(CO)_6-nL[n=1, L=PPh₃（2）, AsPh₃（3）; n=2, L=dppm (4)]. The cluster 2 crystallizes in monoclinic, space group P2₁/n, with a=1.342 4(8) nm, b=1.305 4(8) nm, c=1.875 0(9) nm, β=103.084(9)°, V=3.201(3) nm³, Z=4, F(000)=1 480, D_c=1.515 g·cm^-3, μ=15.62 cm^-1; final R indices [I > 2σ(I)]: R₁=0.040 9, ωR₂=0.076 9; S=1.007, Δρ_max=463e·nm^-3, Δρ_min=-395 e·nm^-3. The cluster 3 crystallizes in monoclinic, space group P2₁/n, with a=1.341 0(4) nm, b=1.307 9(4) nm, c=1.912 0(5) nm, β=103.043(5)°, V=3.267(15) nm³, Z=4, F(000)=1 552, D_c=1.574 g·cm^-3, μ=24.87 cm^-1; final R indices[I> 2σ（I）]：R₁=0.0437, ωR₂=0.078 2; S=0.995, Δρ_max=530 e·nm^-3, Δρ_min=-444 e·nm^-3. CCDC: 221860, 2; 221863, 3.     

Syntheses and molecular structures of new ferrocenylacetylide-bridged binuclear cobalt carbonyl cluster compounds

The reaction of ferrocenylacetylide compounds with Co₂(CO)₈ at room temperature affords four complexes bearing ferrocenyl units with approximately tetrahedral (μ-alkyne)dicobalt moieties [R–(C≡C) _n –R′] [Co₂(CO)₆] _{n ′} [R?=?C₅H₅FeC₅H₄-C(CH₃)₂-C₅H₄FeC₅H₄, R′?=?H, n?=?1, n′?=?1 (1); R?=?C₅H₅FeC₅H₄ [ferrocenyl (Fc)], R′?=?–CH=CHCl, n?=?1, n′?=?1 (2); R?=?Fc, R′?=?Fc, n?=?2, n′?=?1 (3), n′?=?2 (4)]. The compounds were characterized by elemental analysis, IR, ¹H(¹³C) NMR, MS and single-crystal X-ray diffraction analysis. The X-ray analyses show that coordination of the carbon–carbon triple bond and the dicobalt unit result in the formation of a Co₂C₂ tetrahedral core, and the substituents on the acetylenic units show a distortion from linearity that reflects this coordination mode.     

Reactivity of alkynes containing alpha-hydrogen atoms with a triruthenium hydrido carbonyl cluster: alkenyl versus allyl cluster derivatives

The reactions of the hydrido-triruthenium cluster complex [Ru3(mu-H)(mu3-kappa(2)-HNNMe2)(CO)9] (1; H2NNMe2 = 1,1-dimethylhydrazine) with alkynes that have alpha-hydrogen atoms give trinuclear derivatives containing edge-bridging allyl or face-capping alkenyl ligands. Under mild conditions (THF, 70 degrees C) the isolated products are as follows: [Ru3(mu3-kappa(2)-HNNMe2)(mu-kappa(3)-1-syn-Me-3-anti-EtC3H3)(mu-CO)2(CO)6] (2) and [Ru3(mu3-kappa(2)-HNNMe2)(mu-kappa(3)-1-syn-Me-3-syn-EtC3H3)(mu-CO)2(CO)6] (3) from 3-hexyne; [Ru3(mu3-kappa(2)-HNNMe2)(mu-kappa(3)-3-anti-PhC3H4)(mu-CO)2(CO)6] (4), [Ru3(mu3-kappa(2)-HNNMe2)(mu-kappa(2)-MeCCHPh)(mu-CO)2(CO)6] (5) and [Ru3(mu3-kappa(2)-HNNMe2)(mu3-kappa(2)-PhCCHMe)(mu-CO)2(CO)6] (6) from 1-phenyl-1-propyne; [Ru3(mu3-kappa(2)-HNNMe2)(mu-kappa(2)-3-anti-PrC3H4)(mu-CO)2(CO)6] (7), [Ru3(mu3-kappa(2)-HNNMe2)(mu3-kappa(2)-BuCCH2)(mu-CO)2(CO)6] (8), and [Ru3(mu3-kappa(2)-HNNMe2)(mu3-kappa(2)-HCCHBu)(mu-CO)2(CO)6] (9) from 1-hexyne; [Ru3(mu3-kappa(2)-HNNMe2)(mu3-kappa(2)-HOH2CCCH2)(mu-CO)2(CO)6] (10) from propargyl alcohol; and [Ru3(mu3-kappa(2)-HNNMe2)(mu3-kappa(2)-MeOCH2CCH2)(mu-CO)2(CO)6] (11) from 3-methoxy-1-propyne. The regioselectivity of these reactions depends upon the nature of the alkyne reagent, which affects considerably the kinetic barriers of important reaction steps and the stability of the final products. It has been established that the face-capped alkenyl derivatives are not precursors to the allyl products, which are formed via edge-bridged alkenyl intermediates. At higher temperature (toluene, 110 degrees C), the complexes that have allyl ligands with an anti substituent are isomerized into allyl derivatives with that substituent in the syn position, for example, 4 into [Ru3(mu3-kappa(2)-HNNMe2)(mu-kappa(3)-3-syn-PhC3H4)(mu-CO)2(CO)6] (14). The diene complex [Ru3(mu-H)(mu3-kappa(2)-HNNMe2)(mu-kappa(4)-trans-EtC4H5)(CO)7] (13) has been obtained from the thermolysis of compounds 2 and 7 at 110 degrees C (3 and [Ru3(mu3-kappa(2)-HNNMe2)(mu-kappa(2)-3-syn-PrC3H4)(mu-CO)2(CO)6] (12) are also formed in these reactions). A DFT theoretical study has allowed a comparison of the thermodynamic stabilities of isomeric compounds and has helped rationalize the experimental results. Mechanistic proposals for the synthesis of the allyl complexes and their isomerization processes are also provided.     

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 and characterization of novel derivatives of triazinone

Triazinone is a kind of heterocyclic compound with potential biological activity. The molecular design, synthesis and optimization of lead compounds are important to the development of insecticides. Six new triazinone derivatives were synthesized and characterized by IR, ¹H-NMR and MS spectra. The mechanism of synthesis of aminotriazinone was discussed. Translated from Huaxue Tongbao (Chemistry), 2006, 69(9): 674–679 (in Chinese)     

含硫氮杂环卡宾铁羰基簇合物的合成和结构

Fe~3(CO)~1~2与4个S,N取代的杂环硫代酰胺配前体[SCSC(SR)NNPh(SL~n),其中SL~1:R=Me;SL~2:R=Et;SL~3:R=n-Pr;SL~4:R=i-Bu]反应,合成得到含硫氮杂环卡宾配体的通式为[Fe~3(CO)~8(μ~3-S)~2L]的4个新羰合铁簇合物(1～4)。其配体S原子和杂环卡宾L皆来自配前体SL的劈开。对它们进行了元素分析,IR,^1HNMR和MS表征,并用X射线衍射测定了2的晶体分子结构,表明含硫氮杂环分子片CSC(SR)NNPh(L)的卡宾碳具有sp^2成键特征,其C~卡~宾键长为0.1960nm。2的分子几何构型维持母体物[Fe~3(CO)~9(μ~3-S)~2]的形状,其中卡宾基取代四方锥分子骨架Fe~3S~2基底平面Fe(1)S(1)Fe(3)S(2)的Fe(3)原子上径向位置的一个端羰基CO。     

2,9,16,23-四-(2,6-二甲基苯氧基)酞菁钴(Ⅱ)的合成、表征及性质

用4-(2,6-二甲基苯氧基)邻苯二腈和金属盐在熔融状态下合成了2,9,16,23-四-(2,6-二甲基苯氧基)酞菁钴配合物,对产物进行了IR、UV-vis光谱、元素分析、热重分析等测定和表征.