Recent Developments of Tellurium- and Selenium-Containing Iron Carbonyl Clusters

In recent years, quite a number of tellurium-or selenium-containing iron carbonyl clusters have been synthesized and structurally characterized, and some interesting structural transformations and reactivity of these clusters have been systematically investigated as well. The syntheses and reactivity of these clusters are reviewed and compared.     

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.     

Synthesis and Characterization of Manganese Carbonyl Compounds with PNP

Attheendof1930s,ThesynthesisofMn(C6H6)21firstreportedbyH.Gilmanattractedmuchattention.Subsequently,manyneworgano-manganesecompoundshavebeensythesized.Inthe1950s,itwasfoundthatCPMn(CO)3andsomeofitSderivativesaughtactastheantiknockofgasolinetosubstitutetetra-ethylleadwhichisveryharmfultoourenvironment.Thisfindinghasattractedpeople'sinterestinthestudyofthisfield.Inthiswork,weobtainedtwonewcompoundsthroughthesubstitutionreactionbetweenmixeddonorphosphineligand2,6-di(hi-phenylphosphine)pyridme…     

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.     

含面桥基磷硫配体的新颖三核和四核钌羰合簇

[Ru₃(CO)₁₂]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簇[(μ-H)₂Ru₃(CO)₉(μ₃-P)](Ⅰ)和四核钌羰合簇[(Ru₄(CO)₁₀(μ₃-S)(μ₃-PC₆H₄OMe)](Ⅰ).X射线衍射测定了的晶体分子结构,表明含有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的簇合物对氧和水稳定.谱学分析表明,化合物具有四面体型的Ru₄簇心,其三角形面上分别具有面桥基μ₃-S和μ₃-PC₆H₄OMe基配体.     

Diacetylenic Derivatives of Fe2(CO)6(μ-EE′): Spectroscopic Investigations of Fe2(CO)6{μ-EC(H) = C(C≡ CMe)E′} (E = E′, E ≠ E′; E, E′ = S, Se, Te)

The diacetylenic adducts, Fe₂(CO)₆{-EC(H) = C(C CMe)E} (E = E, E E; E, E = S, Se, Te) (1–8) have been obtained from the room temperature stirring of Fe₂(CO)₆(-EE) with HC CC CMe in methanol solvent containing sodium acetate. Compounds 1–8 have been characterized by IR and multinuclear NMR (¹H, ¹³C, ⁷⁷Se, and ^l25Te) spectroscopy. Trends in the chemical shifts of ⁷⁷Se and ¹²⁵Te NMR spectra of Fe₂(CO)₆{-EC(H) = C(C CMe)E} with a variation of EE are discussed.     

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.     

两个基于混酸配体的十二核锰配合物的合成和结构

应用乙酸锰、高锰酸钾和丙酸(或氯乙酸)混酸体系合成,得到了2个基于Mn12O12核心的十二核锰配合物,分子式分别为[Mn12O12(O2CMe)8(O2CEt)8(H2O)4].2H2O(1)和[Mn12O12(O2CMe)12(O2CCl3)4(H2O)4].4MeCO2H.8H2O(2)。X射线单晶衍射分析表明配合物1结晶于四方晶系I4空间群,晶胞参数为:a=b=2.650 5(3)nm,c=1.349 7(3)nm,Z=4;配合物2结晶于四方晶系I41/acd空间群,晶胞参数为:a=b=2.7067(1)nm,c=2.5880(2)nm,Z=8。这2个配合物结构都具备Mn12O12核心,与其他经典Mn12明星分子的核心相似。中心的Mn4O4立方核通过μ3-氧桥被非共面的Mn8O8环聚集在一起,而16个η2-μ-混合羧酸以不同方向在外围充当连接桥,同时提供了酸性环境。文中还分析了混酸体系的pKa值对配合物结构形成的影响。     

Isomerism of [FeMM′(μ3-Q)(CO)7CpCp′] heterometallic clusters (Q = Se, Te; M, M′ = Mo, W; Cp = η5-C5H5; Cp′ = Cp, η5-C5(CH3)5) in solids

The crystal structures of three cluster compounds: [(µ-H)Fe₂Mo(µ₃-Te)(CO)₈Cp*], [FeMo₂(µ₃-Te)(CO)_7x Cp*₂], and [FeMoW(µ₃-Te)(CO)₇CpCp*], where Cp = ⁵-C₅H₅, Cp* = ⁵-C₅ (CH₃)₅, have been investigated. In the cluster with a tetrahedral {FeMo₂Te} core, one can observe positional isomerism of the carbonyl and cyclopentadienyl ligands with respect to the plane through the Fe and Te atoms and the center of the Mo₂bond, resulting in two mirror isomers in the racemic crystal. In the cluster with the {FeMoWTe} core, additional chirality causes the formation of four diastereoisomers. Earlier, the structure of the [FeMoW(µ₃-Se)(CO)₇Cp] cluster with Mo and W atoms coordinated to identical Cp-ligands has been structurally defined. In this crystal, statistical disordering of Mo and W over the metal positions is observed. In the [FeMo(Cp*)W(Cp)(µ₃-Te)(CO)₇] cluster studied here, the Mo and W atoms are coordinated to different cyclopentadienyl ligands. Due to this, two of four diastereoisomers were isolated as ordered racemic crystals; the other two are nonexistent for steric reasons.Original Russian Text Copyright © 2004 by A. V. Virovets, S. N. Konchenko, P. S. Yuferov, and D. FenskeTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 522–527, May–June 2004.     

Structural Interconversion of Bimetallic Carbonyl Clusters ­Induced by a NHC Ligand and Its Selectivity on Fragments

The reactions of IMes‐HCl with bimetallic iron‐copper clusters were investigated and it showed that interconversions among bimetallic Fe_xCu_y(CO)_z^n– clusters were induced by IMes‐HCl. The reaction priority of IMes‐HCl with fragments in Fe_xCu_y(CO)_z^n– was also investigated and the reaction behaviors of zero valent Fe(CO)₄ and divalent Fe(CO)₄ with IMes‐HCl were discussed.     

基于多齿希夫碱配体的四核和十核锰簇合物的合成、结构和磁性

合成了一种具有{NO₄}给电子组成的多齿水杨醛希夫碱配体,3,5-二-叔丁基水杨醛-三(羟甲基)氨基甲烷(H₄L),并利用元素分析、红外光谱以及核磁共振氢谱表征其结构。Mn(ClO₄)₂或MnCl₂·4H₂O分别与该配体在溶液中反应生成了一个四核锰簇合物[Mn₄^Ⅲ(HL)₂(H₂L)₂(MeCN)₄](ClO₄)₂·2MeCN(1)和一个十核锰簇合物[Mn₆^ⅢMn₄^Ⅱ(bz)₁₀(L)₄(H₂O)₂]·10MeCN(2)。X-射线衍射分析表明化合物1的晶体结构空间群为三斜P1,而化合物2为正交Aba2。2~300K温度区间的磁性测量数据表明化合物2中存在反铁磁相互作用。     

基于多齿希夫碱配体的四核和十核锰簇合物的合成、结构和磁性

合成了一种具有{NO₄}给电子组成的多齿水杨醛希夫碱配体,3,5-二-叔丁基水杨醛-三(羟甲基)氨基甲烷(H₄L),并利用元素分析、红外光谱以及核磁共振氢谱表征其结构。Mn(ClO₄)₂或MnCl₂·4H₂O分别与该配体在溶液中反应生成了一个四核锰簇合物[Mn^III₄(HL)₂(H₂L)₂(MeCN)₄](ClO₄)₂·2MeCN(1)和一个十核锰簇合物[Mn^III₆Mn^II₄(bz)10(L)₄(H₂O)₂]·10MeCN(2)。X-射线衍射分析表明化合物1的晶体结构空间群为三斜P1,而化合物2为正交Aba2。2~300 K温度区间的磁性测量数据表明化合物2中存在反铁磁相互作用。     

膦化聚苯乙烯担载四核羰基钴簇的合成和催化作用

合成了两种含膦聚苯乙烯载体和此二载体与四核羰基钴簇CO_4(CO)_8(μ_2-CO_2(μ_4-PPh)_2通过配体交换反应,合成两种担载的金属原子簇催化剂.用IR、VU-DRS和XPS表征担载簇配合物的结构.考察了担载簇催化剂对讣茑烯烃的氢甲酰化反应的催化活性.其活性顺序为:1-庚烯>环己烯>二异丁烯>2-辛烯>苯乙烯.     

Polymerization Isomerism in Co-M (M = Cu,Ag, Au) Carbonyl Clusters: Synthesis,Structures and Computational Investigation

The reaction of [Co(CO)₄]⁻ (1) with M(I) compounds (M = Cu, Ag, Au) was reinvestigated unraveling an unprecedented case of polymerization isomerism. Thus, as previously reported, the trinuclear clusters [M{Co(CO)₄}₂]⁻ (M = Cu, 2; Ag, 3; Au, 4) were obtained by reacting 1 with M(I) in a 2:1 molar ratio. Their molecular structures were corroborated by single-crystal X-ray diffraction (SC-XRD) on isomorphous [NEt₄][M{Co(CO)₄}₂] salts. [NEt₄](3)represented the first structural characterization of 3. More interestingly, changing the crystallization conditions of solutions of 3, the hexanuclear cluster [Ag₂{Co(CO)₄}₄]²⁻ (5) was obtained in the solid state instead of 3. Its molecular structure was determined by SC-XRD as Na₂(5)·C₄H₆O₂, [PPN]₂(5)·C₅H₁₂ (PPN = N(PPh₃)₂]⁺), [NBu₄]₂(5) and [NMe₄]₂(5) salts. 5 may be viewed as a dimer of 3 and, thus, it represents a rare case of polymerization isomerism (that is, two compounds having the same elemental composition but different molecular weights) in cluster chemistry. The phenomenon was further studied in solution by IR and ESI-MS measurements and theoretically investigated by computational methods. Both experimental evidence and density functional theory (DFT) calculations clearly pointed out that the dimerization process occurs in the solid state only in the case of Ag, whereas Cu and Au related species exist only as monomers.     

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)。     

Water‐Soluble Manganese Inorganic Polymers: The Role of Carborane Clusters and Producing Large Structural Adjustments from Minor Molecular Changes

The reaction of two different carboranylcarboxylate ligands, 1‐CH₃‐2‐CO₂H‐1,2‐closo‐C₂B₁₀H₁₀ or 1‐CO₂H‐1,2‐closo‐C₂B₁₀H₁₁, with MnCO₃ in water leads to polymeric compounds 1 a and 1 b . Both compounds have been characterized by analytical and spectroscopic techniques. Additionally, electrochemical techniques have also been used for compound 1 a . X‐ray analysis revealed substantial differences between both compounds: whereas a six‐coordinated Mn^II compound with water molecules bridging two Mn^II centers has been observed for 1 a , a square pyramidal geometry around each Mn^II ion with terminal water molecules coordinated to each Mn^II center has been found for 1 b . The observed differences have been attributed to the existence of different substituents, ?CH₃ or ?H, on one of the carbon atoms of the carboranylcarboxylate ligand. The reaction of 1 a and 1 b with coordinating solvents, such as ethers or Lewis bases, leads to the formation of new compounds with low (mononuclear 4 a , 4 b ; dinuclear 3 a , 3 b ; and trinuclear 2 a ) or high nuclearity (hybrid polymer, 5 a ), due to breakage of the corresponding polymer. X‐ray analysis shows that the structural core present in the polymeric materials is not maintained in the resulting compounds, with the exception of trinuclear compound 2 a . The magnetic properties of the compounds studied show weak antiferromagnetic coupling.     

Designed Construction of Mixed-Metal,Mixed Chalcogenide Clusters

Room temperature reactions between Fe₂(CO)₆(μ-EE'), (E and E' = S, Se or Te) and M(CO)₅(thf), M = Cr, Mo or W yield three types of clusters, the formation of each type clearly dependent on the nature of E and E' present in Fe₂(CO)₆(μ-EE') and on the nature of M in M(CO)₅(thf). While the Mo and W adducts are based on square pyramidal heavy atom cores, the Cr adduct has an unusual structure and can be considered as an inorganic analog of quadricyclane.     

CuSeTeCl,CuSeTeBr und CuSeTeI: Verbindungen mit geordneten [SeTe]-Schrauben

CuSeTeCl, CuSeTeBr, and CuSeTeI: Compounds with ordered [SeTe] Screws The hitherto unknown copper(I) chalcogen halides CuSeTeCl, CuSeTeBr and CuSeTeI have been prepared and their crystal structures were determined. The compounds of general composition CuSeTeX crystallize in the monoclinic system, space group P2₁/n (No. 14), Z = 4, a = 7.9796(9), b = 4.7645(8), c = 10.843(3) Å, β = 104.12(1)°, V = 399.8(1) ų (X = Cl), a = 8.155(3), b = 4.765(2), c = 11.286(4) Å, β = 104.21(3)°, V = 425.1(3) ų (X = Br) and a = 8.4370(9) b = 4.7652(5), c = 11.996(2) Å, β = 103.178(9)°, V = 469.6(1) ų (X = I). The crystal structures show infinite onedimensional screws YY′ of chalcogen atoms, with Y = Se and Y′ = Te alternately. The coordinations of Se and Te in these compounds are quite different.     

Synthesis of clusters Fe2(CO)6(μ-XCH2CH=CH2)(μ3-X)Fe(CO)2Cp (X = Se, S; Cp = η5-C5H5)

The clusters Fe₂(CO)₆(μ-XCH₂CH=CH₂)(μ₃-X)Fe(CO)₂Cp (X = S, Se) were prepared by the successive treatment of the bi- and trimetallic complexes Fe₂(CO)₆(μ-Se₂) and Fe₃(CO)₉(μ₃-X) with allylmagnesium chloride and CpFe(CO)₂I. The clusters obtained contain a noncoordinated C=C bond. The structure of the Se-containing cluster was suggested on the basis of comparison of its spectral data (IR,¹H NMR, and Mössbauer spectra) with the spectra of the analogous S-containing complex, which was previously characterized by X-ray diffraction analysis.     

A Regioselective Synthesis of Novel Functionalized Organochalcogen Compounds by Chalcogenocyclofunctionalization Reactions Based on Chalcogen Halides and Natural Products

The regioselective synthesis of novel functionalized condensed organochalcogen compounds by chalcogenocyclofunctionalization reactions based on chalcogen halides and the natural products thymol and carvacrol has been developed. The reactions of selenium dibromide with allyl thymol and allyl carvacrol proceeded in methylene chloride at room temperature in the presence of NaHCO₃ affording bis[(7-isopropyl-4-methyl-2,3-dihydro-1-benzofuran-2-yl)methyl] and bis[(4-isopropyl-7-methyl-2,3-dihydro-1-benzofuran-2-yl)methyl] selenides in 90–92% yield. Similar sulfides were obtained in 70–72% yields by the reaction of sulfur dichloride in chloroform under reflux. Trihalotellanes containing the same organic moieties were synthesized from allyl thymol, allyl carvacrol and tellurium tetrachloride or tetrabromide in quantitative yields. Corresponding functionalized ditellurides were prepared in 91–92% yields by the reduction of the trichlorotellanes with sodium metabisulfite in two-phase solvent system. The comparison of reactivity of sulfur, selenium and tellurium halides in chalcogenocyclofunctionalization and distinguishing features of each reaction were discussed.