含面桥基磷硫配体的新颖三核和四核钌羰合族

[Ru3(CO12)]与Lawesson试剂[(MeOC6H4PS2)2]反应,合成、分离并用谱学表征了产物三核钌羰合族[(μ-H）2（Ru）（CO）9（μ3-P）](Ⅰ）和四核钌羰合簇[Ru4(CO)10( μ3-PC6H4OM)](Ⅱ）,X射线衍射测定了Ⅰ晶体分子结构,表明Ⅰ含有1个裸磷原子作为面桥基配体,并具有颇短的Ru-Ru键距,该价电子数为49e的族合物对氧和水稳定,谱学分析表明,化合物Ⅱ具有四面体型的Ru4簇心。其三角形面上分别具有面桥基μ3-S和μ3＝PC6H4OMe基配体。     

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)。     

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.     

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.     

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.     

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.     

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.     

R_2dtc为配体的异核过渡金属—硫簇合物研究

本文是作者近年来对R_2dtc为配体的异核过渡金属-硫簇合物的研究工作综述。研究对象包括Mo—Fe—S、W—Fe—S、Mo—Cu—S、W—Cu—S、V—Cu—S组成的四核及四核以上单立方烷、双立方烷、平面型及链状簇合物。综合讨论了它们的合成与结构,提出了R_2dtc配体的结构特点在某些簇骼形成过程中的作用。     

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。     

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。     

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.     

Chemistry of Tetraosmium Carbonyl Clusters with Phenylazopyridine Ligands: Synthesis, Structure and Electrochemistry

Two new tetraosmium carbonyl clusters [Os₄(-H)₄(CO)₁₁{ ¹-NC₅H₄(N=N)C₆H₅}] (1) and [Os₄(-H)₄(CO)₁₀{ ²-NC₅H₄(N=N)C₆H₅}] (2) were synthesized from the reaction of [Os₄(-H)₄(CO)₁₂] with two equivalent of 2-phenylazopyridine ligand in dichloromethane at ambient temperature using trimethylamine-N-oxide as the decarbonylation reagent. Subsequent chromatographic purification led to the isolation of 1and 2as stable orange and blue solids in respectively 25 and 13% yields. Complex 1converted to 2in a 25% yield in refluxing chloroform. Treating a solution of [Os₄(-H)₄(CO)₁₂] in dichloromethane with two equivalent of 3-phenylazopyridine led to the formation of another two new clusters [Os₄(-H)₄(CO)₁₁{ ¹-NC₅H₄(N=N)C₆H₅}] (3) and [Os₄(-H)₄(CO)₁₀(NMe₃){ ¹-NC₅H₄(N=N)C₆H₅}] (4), which could be isolated as yellow solids in 34% and 21% yields respectively. Thermolysis of 3or 4in refluxing n-hexane gives [Os₄(-H)₃(CO)₁₀{- ³-NC₅H₃(N=N)C₆H₅}] (5) in 24 and 33% yields respectively. Their electronic absorption properties and electrochemical behavior are also reported.     

Hydride Migration from a Triangular Face to a Tetrahedral Cavity in Tetranuclear Iron Carbonyl Clusters upon Coordination of [AuPPh3]+ Fragments

Metal hydrides are of fundamental importance in chemistry, both as solid‐state materials and molecular compounds. The first low‐valent molecular metal cluster containing an interstitial four‐coordinate hydride in a tetrahedral site is decribed, which undergoes hydride migration from the surface to the tetrahedral cavity of the cluster upon coordination of a [AuPPh₃]⁺ fragment. The [HFe₄(CO)₁₂(AuPPh₃)₂]^? mono‐anion, which contains a surface μ₃‐H, was obtained from the reaction of [HFe₄(CO)₁₂]^3? with two equivalents of [Au(PPh₃)Cl]. This is, in turn, transformed into the neutral [HFe₄(CO)₁₂(AuPPh₃)₃] upon addition of a third [AuPPh₃]⁺ fragment, with concomitant migration of the unique hydride from the surface of the cluster to its tetrahedral cavity. All of these species have been fully characterized in solution by means of IR and multinuclear NMR spectroscopy, and in the solid state by single‐crystal X‐ray diffractometry.     

Synthesis,Characterization, and Crystal Structures of Diruthenium Complexes Containing Bridging Salicylato Ligands

The thermal reaction of Ru₃(CO)₁₂ ( 1 ) with salicylic acid, in the presence of triphenylphosphine, pyridine, or dimethylsulfoxide, afforded the dinuclear complexes Ru₂(CO)₄(μ‐O₂CC₆H₄OH)₂L₂ ( 2 ) [L = PPh₃ ( 2a ). C₅H₅N ( 2b ); (CH₃)₂SO ( 2c )]. Complex 2b was further reacted with the aromatic dimmines 2,2′‐dipyridine or 1,10‐phenanthroline to give the cationic diruthenium complexes [Ru₂(CO)₂(μ‐CO)₂(μ‐O₂CC₆H₄OH)(N∩N)₂]⁺ ( 3 ) [(N∩N) = 2,2′‐dipyridine ( 3a ); 1,10‐phenanthroline ( 3b )], which were isolated as their tetraphenylborate salts. All five novel complexes were characterized spectroscopically and analytically. For 2a – 2b and 3a – 3b , single‐crystal X‐ray diffraction studies were also carried out.     

Synthesis,Characterization and Crystal Structures of New Difurylphosphido-bridged Dinuclear Ruthenium Carbonyl Complexes Derived from Ferrocenylacetylene Ligands

The difurylphosphido-bridged dinuclear complex [Ru₂(CO)₆(μ-PFu₂)(μ-η¹,η²-Fu)] (Fu = 2-furyl) 1 readily reacts with two equivalents of each of the terminal alkynes HC≡CR (R = Fc, p-C₆H₄Fc, p-C₆H₄NO₂, Fc = Fe(η⁵-C₅H₅)(η⁵-C₅H₄)) by an interesting head-to-tail ynyl coupling with a furan group to form a series of phosphido-bridged diruthenium compounds containing a novel furyl-substituted C₄ hydrocarbyl chain of stoichiometry [Ru₂(CO)₄(μ-PFu₂){μ-η¹,η¹,η²,η³-RCC(H)C(R)C(H)Fu}] (R = Fc 2, p-C₆H₄Fc 3, p-C₆H₄NO₂ 4) in moderate to good yields. Reaction of 1 with an equimolar amount of HC≡CFc and HC≡C(p-C₆H₄NO₂) afforded a pair of isomers of [Ru₂(CO)₄(μ-PFu₂){μ-η¹,η¹,η²,η³-R¹CC(H)C(R²)C(H)Fu}] (R¹ = Fc, R² = p-C₆H₄NO₂ 5a; R¹ = p-C₆H₄NO₂, R² = Fc 5b) together with a small mixture of 4. X-ray crystal structures of 2, 3, 5a and 5b are reported. All of these new alkyne-derived dinuclear complexes are electron precise with 34 cluster valence electrons in which the μ-η¹,η²-furyl ligand acts as a three-electron donor and the μ-phosphido Ru₂ framework is retained in the products upon alkyne coupling reactions. The resulting organic fragment of each complex is coordinated to the Ru atoms via a π, a π-allyl and two σ bonds, and donates seven electrons to the metal core. Dedicated to the memory of Professor F. Albert Cotton.