17685-52-8Relevant articles and documents
Synthesis, structure, and some reactions of the cluster complex [(μ-H)2Fe5(μ3-Se)2(CO) 14]
Bashirov,Pushkarevsky,Vitovets,Fuhr,Konchenko
, p. 739 - 749 (2008)
In the reaction of Na2Se with [Fe(CO)5] in isopropanol with subsequent acidification with HCl, which is used to synthesize [(μ-H)2Fe3(μ3-Se)(CO)9] (II), the cluster [(μ-H)2Fe5(μ3-Se) 2(CO)14] (I) was detected. In assumption that compound I could serve as a suitable synthon for preparing the bulky heterometallic clusters, its reactions with the Rh-containing complexes were studied. The reaction of I with [Rh(CO)2Cp*] (Cp*is pentamethylcyclopentadienyl) was found to give a mixture of the products. The main reaction products were isolated and their structures were determined: [Fe2Rh(μ3-Se)2(CO)6Cp*], [Fe2Rh(μ3-Se)(μ3-CO)(CO) 6Cp*], [FeRh2(μ3-Se)(μ-CO)(CO) 3Cp 2 * ], [Fe2Rh2(μ 4-Se)(μ-CO)4(CO)2Cp 2 * ]. Potassium hydride treatment of II with subsequent addition of [Cp*Rh(CH3CN)3](CF3SO3) 2 leads to the well-known cluster complex [Fe3Rh(μ 4-Se)(CO)9Cp*]. A set of the reaction products indicates that the {Fe5Se2} core cannot be used as one-piece building block in the synthesis of heterometallic clusters.
Surface-Modified Photochemistry. Preparation of Silica-Supported Fe3(CO)12 via Irradiation of Adsorbed Fe(CO)5
Jackson, Robert L.,Trusheim, Mark R.
, p. 6590 - 6596 (1982)
The photochemistry of silica-adsorbed Fe(CO)5 has been studied.IR and UV-visible spectra show that the only significant product is Fe3(CO)12 rather than Fe2(CO)9, which is the product observed following irradiation of Fe(CO)5 in the gas or liquid phase or in solution.Formation of Fe3(CO)12 is discussed in terms of a mechanism involving rapid secondary thermal reactions of a surface-complexed form of Fe(CO)4.
Synthesis and structural characterization of bimetallic iron-nickel carbido cluster complexes
Saha, Sumit,Zhu, Lei,Captain, Burjor
, p. 3465 - 3472 (2010)
In acetonitrile solvent, Fe5(CO)15(μ5- C), 1, reacts with Ni(COD)2 at room temperature to afford the iron-nickel complex Fe5NI(NCMe)(CO)15(μ6-C), 3. The acetonitrile ligand In 3 can be replaced by CO and NH3 to yield Fe5Ni(CO)16(μ6-C), 4, and Fe 5Ni(NH3)(CO)15(μ6-C), 6, respectively. When refluxed In acetonitrile solvent, compound 3 loses a vertex to form the square pyramidal Fe4Ni complex Fe4Ni(NCMe) 2(CO)12(μ5-C), 7. Compound 7 readily converts to Fe4Ni(NCMe)(CO)13(μ5-C), 8, by losing one of Its acetonitrile ligands. Addition of acetonitrile to 8 gives compound 7. When heated to 110 o°C under an atmosphere of CO, both compounds 7 and 8 furnish the octahedral Fe4NI2 complex Fe 4Ni2(CO)15(μ6-C), 9. All six compounds were structurally characterized by single-crystal X-ray diffraction analyses.
The reaction of (μ3-CCO2R)Co2M(CO)8L (M = Co, Mo, W ; L = CO, MeCp ; R = Me, Et) with Na2[Fe(CO)4]. X-ray crystal structure analysis of (EtO2CCCCO2Et)Co4(CO
Wu, He-Ping,Zhao, Zhuan-Yun,Liu, Sheng-Ming,Ding, Er-Run,Yin, Yuan-Qi,Huang, Xiao-Ying,Yu, Kai-Bei
, p. 4117 - 4126 (1996)
The reactions of clusters [(μ3-CCO2Et)Co2M(CO)8(MeCp)][M = Mo (2a), W (2b)], derived from the reactions of (μ3-CCO2Et)Co3(CO)9 with Na[M(CO)3(MeCp)], with N
Cluster expansion reactions of group 6 and 8 metallaboranes using transition metal carbonyl compounds of groups 7-9
Geetharani,Bose, Shubhankar Kumar,Sahoo, Satyanarayan,Varghese, Babu,Mobin, Shaikh M.,Ghosh, Sundargopal
, p. 5824 - 5832 (2011)
The reinvestigation of an early synthesis of heterometallic cubane-type clusters has led to the isolation of a number of new clusters which have been characterized by spectroscopic and crystallographic techniques. The thermolysis of [(Cp*Mo)2B4H4E2] (1: E = S; 2: E = Se; Cp* = η5-C5Me5) in presence of [Fe2(CO)9] yielded cubane-type clusters [(Cp*Mo)2(μ3-E)2B2H(μ-H) {Fe(CO)2}2Fe(CO)3], 4 and 5 (4: E = S; 5: E = Se) together with fused clusters [(Cp*Mo)2B4H 4E2Fe(CO)2Fe(CO)3] (8: E = S; 9: E = Se). In a similar fashion, reaction of [(Cp*RuCO)2B 2H6], 3, with [Fe2(CO)9] yielded [(Cp*Ru)2(μ3-CO)2B2H(μ- H){Fe(CO)2}2Fe(CO)3], 6, and an incomplete cubane cluster [(μ3-BH)3(Cp*Ru) 2{Fe(CO)3}2], 7. Clusters 4-6 can be described as heterometallic cubane clusters containing a Fe(CO)3 moiety exo-bonded to the cubane, while 7 has an incomplete cubane [Ru 2Fe2B3] core. The geometry of both compounds 8 and 9 consist of a bicapped octahedron [Mo2Fe2B 3E] and a trigonal bipyramidal [Mo2B2E] core, fused through a common three vertex [Mo2B] triangular face. In addition, thermolysis of 3 with [Mn2(CO)10] permits the isolation of arachno-[(Cp*RuCO)2B3H7], 10. Cluster 10 constitutes a diruthenaborane analogue of 8-sep pentaborane(11) and has a structural isomeric relationship to 1,2-[{Cp*Ru} 2(CO)2B3H7].
Thermal dissociation of iron carbonyls during growth of iron whiskers
Babin,Belousov,Dobryakova,Nekrasov,Syrkin,Uel'skii
, p. 1903 - 1913 (2004)
Methods for the preparation of iron whiskers in chemical transport reactions of thermal dissociation of iron penta- and dodecacarbonyls and carbidocarbonyl clusters Fe5C(CO)15 were described. The morphology, structure, and chemical composition of the whiskers were studied. The main factors determining the growth rate and mechanical properties of the whiskers were revealed. A model for the mechanism of thermal dissociation of iron carbonyls was proposed. This process was shown to be a chain radical ion reaction initiated via the scheme of activating complex formation. Analogies between the thermal dissociation of iron carbonyls in the adsorption layer and the known radical ion processes in the liquid and gas phases were found.
Deprotonation of ferraborane clusters and their relative acidities
McCarthy,Durie,Embry,Imbur,Marhoefer
, p. 1972 - 1974 (2001)
The relative Bronsted acidities for a series of ferraborane clusters were determined. Relative acidities were studied by proton competition reactions between neutral and anionic species followed by IR spectroscopy. From these studies the relative trend in acidities was determined to be B2H6Fe2(CO)9 3(CO)9BH4 = HFe4(CO)12BH2 3(CO)10BH2.
Stereoselective Double Functionalization of Iron-Carbonyl Complexes of 5,6,7,8-Tetramethylidenebicyclooct-2-ene. Crystal Structure and Absolute Configuration of (-)-trans-μ-<(2S,5R,7S)-C,5,6,C-η:C,7,8,C-η-(6,7,8-trimethylidene-5-((Z)-2-oxopropylide
Tagliaferri, Enrico,Campiche, Philippe,Roulet, Raymond,Gabioud, Raphy,Vogel, Pierre,Chapuis, Gervais
, p. 126 - 134 (1985)
The Friedel-Crafts monoacylation of trans-μ-octyl acetate)>-bis(tricarbonyliron) ((+/-)-5) is highly stereoselective and yields trans-μ-(1RS,2RS,4RS,5SR,6RS,7RS,
Kruger, Gert J.,Lotz, Simon,Linford, Lorna,Van Dyk, Martie,Raubenheimer, Helgard G.
, p. 241 - 252 (1985)
DIPHOSPHOR, PHOSPHOR-, ARSEN- UND ANTIMONATOME ALS CLUSTERBAUGRUPPEN
Lang, Heinrich,Huttner, Gottfried,Zsolnai, Laszlo,Mohr, Gerhard,Sigwarth, Beate,et al.
, p. 157 - 180 (1986)
Reactions of Fe2(CO)9 with LnM-PHal3 (LnM = 16-electron fragment: Cp(CO)2Mn, (CO)5Cr, (CO)5Mo, (CO)5W) yield clusters of the type Fe3(CO)9(μ4-P)2(MLn)2 (II).Compounds II contain the trigonal bipyramidal cluster framework Fe3(CO)9(μ3-P)2, the basis of which is a closed triangle formed by three Fe(CO)3 units; the apical positions of the trigonal bipyramid are occupied by phosphorus atoms.Each of the capping phosphorus atoms binds an additional MLn fragment.Compounds of type II are also obtained from Fe2(CO)6(μ3-P)2(MLn)2 (I) by formal addition of an Fe(CO)3 group.A further general synthetic approach to clusters Fe3(CO)9(μ4-X)2(MLn)2 (X = P, As, Sb) is the reaction of halo-phosphinidene, arsinidene ar stibinidene complexes, (LnM)2X-Hal (X= P, As, Sb) with Na2Fe(CO)4.Similar procedures are used for the construction of compounds II and IV.Complexes III contain phosphorus as a μ4-spiro centre; compounds IV contain metallacyclic phosphanes as ligands.From (CO)5CrPBr3 and Fe2(CO)9 the cluster Fe2(CO)7(PP)2 (V) is obtained in which a diphosphorus unit is side-on and end-on coordinated as an eight-electron ligand.The identity of the new compounds is documented by analytic and spectroscopic data as well as by X-ray-structure analyses of seven compounds.
syn-BIS-DIAZENE ALS MATRICES FUER DEN AUFBAU FLAECHIGER OLIGOMETALL-AGGREGATE
Fischer, G.,Sedelmeier, G.,Prinzbach, H.,Knoll, K.,Wilharm, P.,et al.
, p. 307 - 312 (1985)
Compounds with the syn-bis-diazene structural unit containing two cis-diazene groups in almost parallel orientation to each other may act as matrices for the stabilisation of pentametallic aggregates.The synthesis and structure of (μ5-η4-C11H16N4)Fe5(CO)13 (2) in which an Fe5(CO)13 entity is bound to a syn-bis-diazene ligand is reported.
Crystal Structure and Absolute Configuration of (+)-(1S,2R)-5,6-Dimethylidene-2exo-norbornyl-exo-irontricarbonyl p-Bromobenzoate
Barras, Charles,Roulet, Raymond,Vieira, Eric,Vogel, Pierre,Chapuis, Gervais
, p. 2328 - 2337 (1981)
The title complex (+)-13x has been prepared in an enantiomerically pure form.Its absolute configuration has been determined by single-crystal X-ray diffraction and has been correlated chemically to that of the 5,6-dimethylidene-2-norbornyl derivatives (-)-1, (-)-2, (-)-3 and to (-)-(1S,2R)-benzonorborn-5-en-2-yl acetate (s.Scheme 1), whose configuration was deduced by indirect techniques.A critical analysis of the chiroptical propeties of the exocyclic dienes 1-3 is now possible.These compounds are limiting systems for the application of the allylic axial chirality rule, the generalized octant rule and the symmetry rule for β,γ-unsaturated ketones.
Cyclopentannulation reactions with organoiron reagents. facile construction of functionalized hydroazulenes
Rosenblum,Watkins
, p. 6316 - 6322 (1990)
Troponeiron tricarbonyl, 2-methyltroponeiron tricarbonyl, and 4-methyltroponeiron tricarbonyl are converted to fluxional tropyliumiron tricarbonyl salts by treatment with either trimethylsilyl or di-n-butylboron triflate. These pentadienyliron cations react with (η1-allyl) (η1-propargyl)-, and (η1-allenyl)Fp complexes [Fp = C5H5Fe(CO)2] to give ketohydroazulene cycloadducts derived, in each reaction, from a single tautomeric tropylium cation. The further reaction of two such cycloadducts 14 and 22b with lithium dimethyl cuprate gave tricyclic ketones 25a and b, through a sequence depicted as involving initial formation of an anionic acyliron complex, followed by migratory insertion and an intramolecular aldol condensation.
Novel class of heterometallic cubane and boride clusters containing heavier group 16 elements
Thakur, Arunabha,Sao, Soumik,Ramkumar,Ghosh, Sundargopal
, p. 8322 - 8330 (2012)
Thermolysis of an in situ generated intermediate, produced from the reaction of [CpMoCl4] (Cp* = η5-C 5Me5) and [LiBH4.THF], with excess Te powder yielded isomeric [(CpMo)2B4TeH5Cl] (2 and 3), [(CpMo)2B4(μ3-OEt)TeH3Cl] (4), and [(CpMo)4B4H4(μ4-BH) 3] (5). Cluster 4 is a notable example of a dimolybdaoxatelluraborane cluster where both oxygen and tellurium are contiguously bound to molybdenum and boron. Cluster 5 represents an unprecedented metal-rich metallaborane cluster with a cubane core. The dimolybdaheteroborane 2 was found to be very reactive toward metal carbonyl compounds, and as a result, mild pyrolysis of 2 with [Fe2(CO)9] yielded distorted cubane cluster [(CpMo)2(BH)4(μ3-Te){Fe(CO)3}] (6) and with [Co2(CO)8] produced the bicapped pentagonal bipyramid [(CpMoCo)2B3H2(μ3-Te) (μ-CO){Co3(CO)6}] (7) and pentacapped trigonal prism [(CpMoCo)2B3H2(μ3-Te)(μ-CO) 4{Co6(CO)8}] (8). The geometry of 8 is an example of a heterometallic boride cluster in which five Co and one Mo atom define a trigonal prismatic framework. The resultant trigonal prism core is in turn capped by two boron, one Te, and one Co atom. In the pentacapped trigonal prism unit of 8, one of the boron atoms is completely encapsulated and bonded to one molybdenum, one boron, and five cobalt atoms. All the new compounds have been characterized in solution by IR, 1H, 11B, and 13C NMR spectroscopy, and the structural types were unambiguously established by crystallographic analysis of 2 and 4-8
Surface-supported Metal Carbonyl Clusters: Formation of - by Interaction of Fe3(CO)12 and Fe(CO)5 with Alumina and Magnesia
Hugues, Francois,Smith, A. K.,Taarit, Y. Ben,Basset, J. M.
, p. 68 - 70 (1980)
Interaction of Fe3(CO)12 and Fe(CO)5 with the surface of alumina and magnesia results in the formation of the anionic hydrido cluster carbonyl -M+, M+ = Al(O-)x+ or Mg(O-)y
Novel carbonyl iron-bismuth clusters - Synthesis, structure, CO2 insertion and potential as molecular precursors for BiFeO3
Wójcik, Katarzyna,Rüffer, Tobias,Lang, Heinrich,Auer, Alexander A.,Mehring, Michael
, p. 1647 - 1651 (2011/05/28)
The reaction of Fe2(CO)9 with Bi(OSiMe 2tBu)3 gave soluble [(CO) 4FeBi(OSiMe2tBu)]2 (1) in moderate yield whereas in case of Bi(OtBu)3 used as starting material both [(CO)4FeBi(OtBu)]n (2) and the bismuth-iron cluster [(CO)3FeBi3(OtBu) 4{OCO(OtBu)}]2 (3) were isolated. The latter forms upon insertion of CO2, released during reaction of diiron nonacarbonyl with bismuth tert-butoxide, into a Bi-OtBu bond. The compounds were characterized by IR and 1H NMR spectroscopy as well as thermogravimetric analyses. Additionally, the molecular structures of compounds 1 and 3 were elucidated by single crystal X-ray diffraction. The core structure of [(CO)4FeBi(OSiMe2tBu)]2 (1) is build up by a four-membered Bi2Fe2 ring whereas [(CO) 3FeBi3(OtBu)4{OCO(O tBu)}]2 (3) is composed of two tetrahedral FeBi 3 cluster cores that dimerise via bridging -OCO(OtBu) ligands. Analysis of the TGA residues by PXRD revealed that compound 2 is the best precursor for multiferroic BiFeO3 among the compounds studied here, although Bi25FeO39 was detected as minor impurity.
