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1.
The reaction of [Fe3(CO)12] with bis[2‐(diphenylphosphino)phenyl]ether (DPEphos) in refluxing THF afforded a mononuclear complex, [Fe(CO)4(η1‐P‐DPEphos)] (1), as major product and a binuclear complex, [Fe2(CO)6(μ‐CO)(μ‐P,P‐DPEphos)] (2), as minor product respectively. The DPEphos ligand acts as a terminal P‐donor in complex 1 and a bridging P,P‐donor in complex 2. Complexes 1 and 2 were characterized by elemental analysis, fast atom bombardment mass spectrometry, FT‐IR, 1H and 31P{1H} NMR spectroscopy. The structure of complex 1 has been tentatively assigned by density functional theory calculations and its analogy with reported complexes. Combination of complex 1 and PdCl2 furnished an active catalyst for the Suzuki–Miyaura cross‐coupling reactions of various aryl halides with arylboronic acids. Interestingly, under the same experimental condition, complex 1/PdCl2 as catalyst showed superior activity over the DPEphos/PdCl2 system. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
2.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(1):90-98
The two‐step one‐pot oxidative decarbonylation of [Fe2(S2C2H4)(CO)4(PMe3)2] ( 1 ) with [FeCp2]PF6, followed by addition of phosphane ligands, led to a series of diferrous dithiolato carbonyls 2 – 6 , containing three or four phosphane ligands. In situ measurements indicate efficient formation of 1 2+ as the initial intermediate of the oxidation of 1 , even when a deficiency of the oxidant was employed. Subsequent addition of PR3 gave rise to [Fe2(S2C2H4)(μ‐CO)(CO)3(PMe3)3]2+ ( 2 ) and [Fe2(S2C2H4)(μ‐CO)(CO)2(PMe3)2(PR3)2]2+ (R=Me 3 , OMe 4 ) as principal products. One terminal CO ligand in these complexes was readily substituted by MeCN, and [Fe2(S2C2H4)(μ‐CO)(CO)2(PMe3)3(MeCN)]2+ ( 5 ) and [Fe2(S2C2H4)(μ‐CO)(CO)(PMe3)4(MeCN)]2+ ( 6 ) were fully characterized. Relevant to the Hred state of the active site of Fe‐only hydrogenases, the unsymmetrical derivatives 5 and 6 feature a semibridging CO ligand trans to a labile coordination site. 相似文献
3.
[Fe2(μsb‐CO)(CO)3(NO)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)]: Synthesis, X‐ray Crystal Structure and Isomerization Na[Fe2(μ‐CO)(CO)6(μ‐PtBu2)] ( 1 ) reacts with [NO][BF4] at —60 °C in THF to the nitrosyl complex [Fe2(CO)6(NO)(μ‐PtBu2)] ( 2 ). The subsequent reaction of 2 with phosphanes (L) under mild conditions affords the complexes [Fe2(CO)5(NO)L(μ‐PtBu2)], L = PPh3, ( 3a ); η‐dppm (dppm = Ph2PCH2PPh2), ( 3b ). In this case the phosphane substitutes one carbonyl ligand at the iron tetracarbonyl fragment in 2 , which was confirmed by the X‐ray crystal structure analysis of 3a . In solution 3b loses one CO ligand very easily to give dppm as bridging ligand on the Fe‐Fe bond. The thus formed compound [Fe2(CO)4(NO)(μ‐PtBu2)(μ‐dppm)] ( 4 ) occurs in solution in different solvents and over a wide temperature range as a mixture of the two isomers [Fe2(μsb‐CO)(CO)3(NO)(μ‐PtBu2)(μ‐dppm)] ( 4a ) and [Fe2(CO)4(μ‐NO)(μ‐PtBu2)(μ‐dppm)] ( 4b ). 4a was unambiguously characterized by single‐crystal X‐ray structure analysis while 4b was confirmed both by NMR investigations in solution as well as by means of DFT calculations. Furthermore, the spontaneous reaction of [Fe2(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 5 ) with NO at —60 °C in toluene yields a complicated mixture of products containing [Fe2(μ‐CO)(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 6 ) as main product beside the isomers 4a and 4b occuring in very low yields. 相似文献
4.
The carbamoyl complex [C(NMe2)3][(CO)4Fe{C(O)NMe2}] ( 1 ) reacts with InMe3 under loss of the methyl groups to produce a variety of compounds from which only the anionic cluster complexes [C(NMe2)3]3[Fe2(CO)6(μ‐CO){μ‐InFe(CO)4(μ‐O2CNMe2)InFe(CO)4}] ([C N 3]3[ 2 ]) and [C(NMe2)3]2[{(CO)4Fe}2In(O2CNMe2)]·THF ([C N 3]2[ 3 ]·THF) could be crystallized and characterized by X‐ray analyses. The anion [ 2 ]3? has a Fe2(CO)9‐like structure and both anions contain the carbaminato ligand either in a bridging or in a chelating function. 相似文献
5.
Yue Zhang You‐Tao Si Ming‐Qiang Hu Chang‐Neng Chen Qiu‐Tian Liu 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(11):m499-m500
The novel title double‐butterfly Fe/S cluster complex, [Fe4(C4H8S2)2(CO)12], which is structurally similar to the active site of the Fe‐only hydrogenases, contains two inversion‐related Fe2S2(CO)6 subcluster cores connected by two equivalent butyl chains to afford a 16‐membered macrocycle. The formation of the 16‐membered macrocycle has an influence on the C—S—Fe angles, while the Fe—Fe and Fe—S bond lengths remain similar to those in related complexes. 相似文献
6.
Addition of Cationic Lewis Acids [M′Ln]+ (M′Ln = Fe(CO)2Cp, Fe(CO)(PPh3)Cp, Ru(PPh3)2Cp, Re(CO)5, Pt(PPh3)2, W(CO)3Cp to the Anionic Thiocarbonyl Complexes [HB(pz)3(OC)2M(CS)]− (M = Mo, W; pz = 3,5‐dimethylpyrazol‐1‐yl) Adducts from Organometallic Lewis Acids [Fe(CO)2Cp]+, [Fe(CO)(PPh3)Cp]+, [Ru(PPh3)2Cp]+, [Re(CO)5]+, [ Pt(PPh3)2]+, [W(CO)3Cp]+ and the anionic thiocarbonyl complexes [HB(pz)3(OC)2M(CS)]− (M = Mo, W) have been prepared. Their spectroscopic data indicate that the addition of the cations occurs at the sulphur atom to give end‐to‐end thiocarbonyl bridged complexes [HB(pz)3(OC)2MCSM′Ln]. 相似文献
7.
Ignacio Fernndez PaulS. Pregosin Alberto Albinati Silvia Rizzato UrsulaE. Spichiger‐Keller Tomas Nezel JorgeF. Fernndez‐Snchez 《Helvetica chimica acta》2006,89(8):1485-1496
The addition of primary amines as solubilizing reagents for phthalocyaninatoiron complexes is shown to afford six‐coordinate bis(amine)phthalocyaninato complexes, i.e., [Fe(amine)2(pc)] 2 (amine = decan‐1‐amine) and 3 (amine = benzylamine), with the two new N‐donors occupying the trans‐axial positions. The new complexes were characterized by extensive NMR measurements in THF solution. For complex 3 with the benzylamine ligand, the solid‐state structure was determined by X‐ray diffraction methods. Complex 2 is sufficiently labile in THF solution to exchange one amine ligand against CO (gas) affording an equilibrium mixture containing [Fe(amine)(CO)(pc)] 4 . 相似文献
8.
Reactions of Nitrosyl Complexes. XIII. Synthesis of Novel Di- and Trinuclear Heterobimetallic Complexes with Bridging NO Ligands By reaction of [{Cp′Fe(μ-NO)}2] with [Cp′Mn(CO)2 · (THF)] (Cp′ = μ5-C5H4Me) in THF [Cp3′Fe2Mn(μ-CO)2(μ-NO) · (μ3-NO)] 1 is formed in high yield. The reaction of [{Cp′Fe(μ-NO)}2]Na with [Cp′Mn(CO)2NO]BF4 in DME/acetone yields besides known [{Cp′Mn(CO)(NO)}2] 2 the novel complex [Cp2′FeMn(μ-NO)2NO] 3 . By interaction between [Cp′Mn(CO)2(THF)] and 3 , [Cp3′FeMn2(μ-CO)(μ-NO)2 · (μ3-NO)] 4 is formed. The complex 4 represents the hitherto unknown missing link in the series of the isoelectronic clusters [Cp3′Mn3(μ-NO)3(μ3-NO)], 1 , and [Cp3′Fe3(μ-CO)3(μ3-NO)]. Attempts to synthesize the unknown complex [(Cp′FeNO)2 · Cr(CO)5] by addition of carbene analogous Cr(CO)5 fragments to the Fe=Fe bond in [{Cp′Fe(μ-NO)}2] only led to very low yields of [Cp2′FeCr(CO)5] 5 . The new complexes were characterized by mass, NMR and IR spectra. 相似文献
9.
Mario Ulises Delgado‐Jaime Prof. Serena DeBeer Prof. Matthias Bauer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(47):15888-15897
Valence‐to‐core X‐ray emission spectroscopy (V2C XES) has been applied to a series of compounds relevant to both homogeneous catalysts and intermediates in heterogeneous reactions, namely [Fe(CO)5], [Fe2(CO)9], [Fe3(CO)12], [Fe(CO)3(cod)] (cod=cyclo‐octadienyl), [Fe2Cp2(CO)4] (Cp=cyclo‐pentadienyl), [Fe2Cp*2(CO)4] (Cp*=tetramethylcyclopentadienyl), and [FeCp(CO)2(thf)][B(ArF)4] (ArF=pentafluorophenyl). DFT calculations of the V2C XES spectra show very good agreement with experiment, which allows for an in depth analysis of the origins of the observed spectral signatures. It is demonstrated that the observed spectral features can be broken down into specific ligand and metal fragment contributions. The relative intensities of the observed features are further explained through a quantitative investigation of the metal 3p and 4p contributions to the spectra. The ability to use V2C XES to separate carbonyl, hydrocarbon, and solvent contributions is highlighted. 相似文献
10.
Polynuclear Complexes with Fe? As, Fe? Sb, and Fe? Bi Frameworks The anionic iron clusters Fe3(CO)112? and Fe4(CO)132? were reacted with compounds EX3 and with organic derivatives REX2 and R2EX of the elements arsenic, antimony, and bismuth. Commonly redox and cluster degradation reactions were observed. The new complexes [(CO)4Fe? AsMe2? Fe(CO)4]?, [HFe3(CO)9(mu;3-SbBut)]?, [Fe3(CO)10 (mu;3-Sb)]?, and [Fe3(CO)10(mu;3-Bi)]? were formed and isolated as their PPN salts. The Fe? As? Fe complex was identified by a structure determination, the other complexes were identified by their spectra. 相似文献
11.
Syntheses and Structure Elucidations of Novel (Ironcarbonyl)zinc and ‐cadmium Chloride Derivatives Reactions of zinc/cadmium chloride with Na2[Fe(CO)4] lead to a number of new (iron carbonyl)zinc/cadmium chlorides, wherein the reaction course depends on the used solvent used. In the reaction of ZnCl2 with Na2[Fe(CO)4], three new substances can be prepared. The compound [Zn2Cl2Fe(CO)4(THF)2] ( 1 ), which consists of neutral polymeres, is formed in THF, the ionic compound [Na(DME)3][Zn2Cl3Fe(CO)4] ( 2 ) forms in DME, and from a mixture of THF and TMEDA the compound [Zn2Cl2Fe(CO)4(TMEDA)2] ( 3 ) is obtained as a monomere. Also by using CdCl2, the reaction with Na2[Fe(CO)4] in THF leads to the polymeric compound ([(Cd4Cl6)Fe(CO)4(THF)5] ( 4 )). Carrying out the reaction in a mixture of toluene and DME leads to the formation of the ionic compound [Na(DME)3]2[Cd6{Fe(CO)4}6Cl2(DME)2] ( 5 ) in which an annular dianion consisting of twelve metal atoms is found. From an aqueous solution and subsequent work‐up in THF, the compound [Fe(THF)4(H2O)2][Cd8{Fe(CO)4}4Cl9(THF)6]2 ( 6 ) can be prepared which contains an cluster anion that is built of anellated six membered rings. 相似文献
12.
The reaction of Fe3(CO)12 with (C3H5)2NCS2K in THF at room temperature afforded a red‐brown solution. Treatment of the thus‐obtained solution with MeI and PhCH2Br afforded clusters 1 , (μ‐MeS)Fe2(CO)6(μ4‐S)Fe2(CO)6(μ‐CN(C3H5)2), and 2 , (μ‐PhCH2CO)Fe2(CO)6(μ4‐S)Fe2(CO)6(μ‐CN(C3H5)2). Their structures were unambiguously determined by X‐ray crystallography. Therefore, this methodology provides a novel route for the syntheses of spiro‐S Fe/S clusters with aminocarbyne ligands. 相似文献
13.
Ulf‐Peter Apfel Helmar Görls Greg A. N. Felton Dennis H. Evans Richard S. Glass Dennis L. Lichtenberger Wolfgang Weigand 《Helvetica chimica acta》2012,95(11):2168-2175
(Bis‐selenolato) and (bis‐tellurolato)diiron complexes [2Fe2E(Si)] were prepared and compared with the known (bis‐thiolato)diiron complex A to assess their ability to produce hydrogen from protons. Treatment of [Fe3(CO)12] with 4,4‐dimethyl‐1,2,4‐diselenasilolane ( 1 ) in boiling toluene afforded hexacarbonyl{μ‐{[1,1′‐(dimethylsilylene)bis[methaneselenolato‐κSe : κSe]](2 ?)}}diiron(Fe? Fe) ( 2 ). The analog bis‐tellurolato complex hexacarbonyl{μ‐{[1,1′‐(dimethylsilylene)bis[methanetellurolato‐κTe : κTe]](2 ?)}}diiron(Fe? Fe) ( 3 ) was obtained by treatment of [Fe3(CO)12] with dimethylbis(tellurocyanatomethyl)dimethylsilane, which was prepared in situ. All compounds were characterized by NMR, IR spectroscopy, mass spectrometry, elemental analysis and single‐crystal X‐ray analysis. The electrocatalytic properties of the [2Fe2X(Si)] (X=S, Se, Te) model complexes A, 1 , and 2 towards hydrogen formation were evaluated. 相似文献
14.
Transition Metal Phosphido Complexes. XIII. P-functional Phosphido-Bridged Heterobimetallic Complexes with and without a Metal-Metal Bond; P(SiMe3)2-Bridged cp(CO)xFe Derivatives cp(CO)2FeP(SiMe3)2 1 reacts with the carbonyl nitrosyl complexes Co(CO)3(NO), Fe(CO)2(NO)2,Mn(CO)(NO)3 substituting a CO ligand and with the THF complexes M′(CO)5THF(M′ = Cr, Mo, W), Mncp(CO)2THF MnMecp(CO)2 which can be obtained in solution substituting the THF ligand to give the phosphido-bridged bimetallic complexes cp(CO)2Fe[μ-P(SiMe3)2]M′Lm 2 (M′Lm = Co(CO)2(NO) b , Fe(CO)(NO)2 c , Mn(NO)3 d , Cr(CO)5 f , Mo(CO)5 g , W(CO)5 h , Mncp(CO)2 i , MnMecp(CO)2 j ). Solutions of Li(Me3Si)2PM′Lm 4e–l (M′Lm = Fe(CO)4 e , Crcp(CO)(NO) k , Vcp(CO)3 l ) are available by a selective cleavage reaction of a Si? P bond in the complexes (Me3Si)3PM′Lm 3e–l using n-BuLi. Reactions of cp(CO)2FeBr with 4e–l give the bimetallic complexes 2e–l . The open-chain complexes 2c, 2f, 2h–k undergo a photochemical decarbonylation reaction to form the phosphido-bridged bimetallic complexes cp(CO)Fe[μ-CO, μ-P(SiMe3)2]M′Lm?1(Fe-M′) 5 (M′Lm?1 = Fe(NO)2 c , Cr(CO)4 f , W(CO)4 h , Mncp(CO) i , MnMecp(CO) j , Crcp(NO) k ) containing a metal-metal bond. Equilibria between various isomers can partially be observed in solutions of the complexes 5. I.R., N.M.R., and mass spectral data are reported. 相似文献
15.
The reaction of Na2[Fe(CO)4] with Br2CF2 in n‐pentane generates a mixture of the compounds (CO)3Fe(μ‐CO)3–n(μ‐CF2)nFe(CO)3 ( 2 , n = 2; 3 , n = 1) in low yields with 3 as the main product. 3 is obtained free from 2 by reacting Br2CF2 with Na2[Fe2(CO)8]. The non‐isolable monomeric complex (CO)4Fe=CF2 ( 1 ) can probably considered as the precursor for 2 . 3 reacts with PPh3 with replacement of two CO ligands to form Fe2(CO)6(μ‐CF2)(PPh3)2 ( 4 ). The complexes 2 – 4 were characterized by single crystal X‐ray diffraction. While the structure of 2 is strictly similar to that of Fe2(CO)9, the structure of 3 can better be described as a resulting from superposition of the two enantiomers 3 a and 3 b with two semibridging CO groups. Quantum chemical DFT calculations for the series (CO)3Fe(μCO)3–n(μ‐CF2)nFe(CO)3 (n = 0, 1, 2, 3) as well as for the corresponding (μ‐CH2) derivatives indicate that the progressively larger σ donor and π acceptor properties for the bridging ligands, in the order CO < CF2 < CH2, favor a stronger Fe–Fe bond. 相似文献
16.
Oussama M. El-Kadri 《Journal of organometallic chemistry》2009,694(24):3902-2564
Treatment of M(allyl)(Cl)(CO)2(py)2 (M = Mo, W) with 1 equiv. of potassium pyrazolates in tetrahydrofuran at −78 °C afforded M(allyl)(R2pz)(CO)2(py)n (R2pz = 3,5-disubstituted pyrazolate; n = 1, 2) in 68-81% yields. X-ray crystal structure analyses of Mo(allyl)((CF3)2pz)(CO)2(py)2 and W(allyl)(tBu2pz)(CO)2(py) revealed η1- and η2-coordination of the (CF3)2pz and tBu2pz ligands, respectively. Analogous treatment of Mo(allyl)(Cl)(CO)2(NCCH3)2 with 1 equiv. of tBu2pzK in tetrahydrofuran at −78 °C afforded [Mo(allyl)(tBu2pz)(CO)2]2 in 79% yield. An X-ray crystal structure analysis of [Mo(allyl)(tBu2pz)(CO)2]2 showed a dimeric structure bridged by two μ-η2:η1-tBu2pz ligands. Treatment of M(allyl)(Cl)(CO)2(py)2 with 1 equiv. of lithium 1,3-diisopropylacetamidinate or lithium 1,3-di-tert-butylacetamidinate in diethyl ether at −78 °C afforded M(allyl)(iPrNC(Me)NiPr)(CO)2(py) and M(allyl)(tBuNC(Me)NtBu)(CO)2(py), respectively, in 68-78% yields. The new complexes were characterized by spectral and analytical methods and by X-ray crystal structure determinations. M(allyl)(iPrNC(Me)NiPr)(CO)2(py) adopt pseudo-octahedral geometry about the metal centers, with the 1,3-diisopropylacetamidate ligand nitrogen atoms spanning one axial site and one equatorial site of the octahedron. By contrast, M(allyl)(tBuNC(Me)NtBu)(CO)2(py) adopt pseudo-octahedral structures in which the two 1,3-di-tert-butylacetamidinate ligand nitrogen atoms span two equatorial coordination sites. Sublimation of M(allyl)(tBuNC(Me)NtBu)-(CO)2(py) at 105 °C/0.03 Torr afforded ?7% yields of M(allyl)(tBuNC(Me)NtBu)(CO)2, along with sublimed M(allyl)(tBuNC(Me)NtBu)(CO)2(py). W(allyl)(tBuNC(Me)NtBu)(CO)2 exists in the solid state as a 16-electron complex with distorted square pyramidal geometry. Many of the new complexes undergo dynamic ligand site exchange in solution, and these processes were probed by variable temperature 1H NMR spectroscopy. The volatilities and thermal stabilities were evaluated to determine the potential of the new complexes for use as precursors in thin film growth experiments. 相似文献
17.
The reactions of Fe(CO)5 or Fe3(CO)12 with NaBEt3H or KB[CH(CH3)C2H5]3H, respectively and treatment of the resulting carbonylates M2Fe(CO)4, M = Na, K with elemental selenium in appropriate ratios lead to the formation of M2[Fe2(CO)6(μ‐Se)2]. Subsequent reactions with organo halides or the complex fragment cpFe(CO)2+, cp = η5‐C5H5 afforded the selenolato complexes [Fe2(CO)6(μ‐SeR)2], R = CH2SiMe3 ( 1 ), CH2Ph ( 2 ), p‐CH2C6H4NO2 ( 3 ), o‐CH2C6H4CH2 ( 4 ) and cpFe(CO)2+ ( 5 ) in moderate to good yields. A similar reaction employing Ru3(CO)12, Se and p‐O2NC6H4CH2Br leads to the formation of the corresponding organic diselenide. The X‐ray structures of 1 , 3 , 4 and 5 were determined and revealed butterfly structures of the Fe2Se2 cores. The substituents in 1 , 3 and 5 adopt different conformations depending on their steric demand. In 4 , the conformation is fixed because of the chelate effect of the ligand. The Fe–Se bond lengths lie in the range 235 to 240 pm, with corresponding Fe–Fe bond lengths of 254 to 256 pm. The 77Se NMR data of the new complexes are discussed and compared with the corresponding data of related complexes. 相似文献
18.
Although [Fe(CO)3(CNAr)2] complexes fail to react with dicyclopentadiene at 140°C, under the same conditions [Fe(CO)4(CNAr)] complexes give high yields of [Fe2(η-C5H5(CO)3(CNAr)] and [Fe2(η-C5H5)2(CO)2-(CNAr)2], with the product ratios depending very much on the aryl group (Ar). 相似文献
19.
A diiron hexacarbonyl complex containing bridging phenanthrene‐4,5‐dithiolate ligand is prepared by oxidative addition of Phenanthro[4,5‐cde][1,2]dithiin to Fe2(CO)9. The complex is investigated as a model for the active site of the [Fe–Fe] hydrogenase enzyme. The compound, [(μ‐PNT)Fe2(CO)6]; (PNT = phenanthrene‐4,5‐dithiolate), was characterized by spectroscopic methods (IR, UV/Vis and NMR) and X‐ray crystallography. The IR and proton NMR spectra of [(μ‐PNT)Fe2(CO)6] ( 4 ) are in agreement with a PNT ligand attached to a Fe2(CO)6 core. The infrared spectrum of 4 recorded in dichloromethane contains three peaks at 2001, 2040, and 2075 cm–1 corresponding to the stretching frequency of terminal metal carbonyls. X‐ray crystallographic study unequivocally confirms the structure of the complex having a butterfly shape with an Fe–Fe bond length of 2.5365 Å close to that of the enzyme (2.6 Å). Electrochemical properties of [(μ‐PNT)Fe2(CO)6] have been investigated by cyclic voltammetry. The cyclic voltammogram of [(μ‐PNT)Fe2(CO)6] recorded in acetonitrile contains one quasi‐irreversible reduction (E1/2 = –0.84 V vs. Ag/AgCl, Ipc/Ipa = 0.6, ΔEp = 131 V at 0.1 V · s–1) and one irreversible oxidation (Epa = 0.86 V vs. Ag/AgCl). The redox of [(μ‐PNT)Fe2(CO)6] at E1/2 = –0.84 V can be assigned to the one‐electron transfer processes; [FeI–FeI] → [FeI–Fe0] and [FeI–Fe0] → [FeI–FeI]. 相似文献
20.
A. Abel Lozano M. Dolores Santana Gabriel García J. Elaine Barclay Sin C. Davies David J. Evans 《无机化学与普通化学杂志》2005,631(11):2062-2066
A series of heteronuclear nickel‐iron complexes [Fe2(CO)6(μ‐SH)(μ3‐S){NiCl(PPh3)2}] ( 1 ), [Fe2(CO)6(μ‐SH)(μ3‐S){NiCl(dppe)}] ( 2 ), [Fe2(CO)6(μ3‐S)2{Ni(PPh3)2}] ( 3 ), [Fe2(CO)6(μ3‐S)2{Ni(dppe)}] ( 4 ) and [Fe2(CO)6(μ‐SPh)(μ3‐S){NiCl(dppe)}] ( 5 ) have been prepared. The structure of 4 has been determined by X‐ray crystallography. The central metal‐sulfur core of 4 has a trigonal bipyramidal shape with a NiFe2 base plane with two axial sulfur atoms. Each iron atom is 5‐coordinate forming a distorted square pyramid; the nickel is square planar coordinated by two sulfur atoms and two phosphorus atoms. 相似文献