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1.
Reaction of complex [(μ-SCH2)2NCH2CO2Me]Fe2(CO)6 (A) with 1,1′-bis(diphenylphosphino)ferrocene (dppf) in the presence of the decarbonylating agent Me3NO?2H2O gave complex [(μ-SCH2)2NCH2CO2MeFe2(CO)5]2[(η 5-Ph2PC5H4)2Fe] (1) in 72 % yields, whereas complex [(μ-SCH2)2NPhFe2(CO)5]2[(η 5-Ph2PC5H4)2Fe] (2) was produced by reaction of [(μ-SCH2)2NPh]Fe2(CO)6 (B) with dppf in toluene at reflux in 41 % yield. The new complexes 1 and 2 were characterized by elemental analysis, IR, and 1H (31P, 13C) NMR spectroscopy as well as by single crystal X-ray diffraction analysis. In the crystal structures of 1 and 2, the dppf ligand resides in an apical position of the square-pyramidal geometry of the neighbouring Fe atoms and the crystal structures were stabilized by the intermolecular C–H···O hydrogen bonds. 相似文献
2.
As the active site model of [FeFe]-hydrogenases, complexes [(μ-PDT)Fe2(CO)5]2(dppb) (PDT = SCH2CH2CH2S, dppb = Ph2PCH2CH2CH2CH2PPh2) (1) and [(μ-SCH2)2NCH2CO2Me]Fe2(CO)5(dppm) (dppm = Ph2PCH2PPh2) (2) were prepared by reactions of (μ-PDT)Fe2(CO)6 (A) or [(μ-SCH2)2NCH2CO2Me]Fe2(CO)6 (B) with dppb or dppm in the presence of the decarbonylating agent Me3NO?2H2O in MeCN at room temperature. Complex 1 was characterized by elemental analysis, IR, and 1H (31P, 13C) NMR spectroscopic techniques. In addition, the molecular structures of 1 and 2 have been confirmed by single crystal X-ray diffraction analysis. In the crystal structure of 1, two phosphorus atoms of dppb reside in a basal position of the square-pyramidal coordination sphere of the Fe2 and Fe3 atoms. However, in the crystal structure of 2, P1 atom of dppm resides in an apical position of the square-pyramidal coordination sphere of the Fe2 atom. 相似文献
3.
Reaction of the diiron propanedithiolate complex [μ-(SCH2)2CHC6H5]Fe2(CO)6 (A) with 1,3-bis(diphenylphosphine)propane (dppp) in refluxing xylene yielded a chelated complex [(μ-SCH2)2CHC6H5]Fe2(CO)4(κ2-dppp) (1) and a bridged isomer [(μ-SCH2)2CHC6H5]Fe2(CO)4(μ-dppp) (2), while in refluxing toluene or in hot MeCN in the presence of Me3NO·2H2O gave the chelated isomer 1 as the major or sole product. Protonation of complex 1 upon addition of HBF4·Et2O gave a bridging hydride (μ-H)[(μ-SCH2)2CHC6H5]Fe2(CO)4(κ2-dppp)(BF4) (3). The structures of all complexes were fully characterized by spectroscopic methods and for complexes 1 and 2 by X-ray crystallography. In the solid state, the chelated complex adopts an apical–basal diphosphine arrangement and exhibits a six-membered ring in approximate chair conformation. The bridged isomer presents an expected cisoid dibasal geometry and the bond length of Fe–Fe is longer than that in chelated isomer, reaching to 2.61 ?. The electrochemical investigation of both isomers in MeCN-[NBu4][PF6] in the presence of HBF4 showed that the catalytic efficiency of the bridged isomer is no less than that of the chelated isomer but better than that of the analogue [(μ-SCH2)2CHC6H5]Fe2(CO)4(μ-dppm). Interestingly, isomer 1 was converted to isomer 2 in refluxing xylene. An electron-transfer-catalyzed isomerization between one isomer and the other was not observed. 相似文献
4.
The hydroxyl- and pyridyl-functionalized diiron azadithiolate complexes [{(μ-SCH2)2N(CH2CH2OH)}Fe2(CO)6] (1) and [{(μ-SCH2)2N(CH2CH2OOCPy)}Fe2(CO)6] (Py = pyridyl) (2) were prepared as biomimetic models of the active site of Fe-only hydrogenases. Both complexes were characterized by MS, IR, 1H NMR spectra and elemental analysis. The molecular structures of 1 and 2 were determined by single crystal X-ray analysis. A network is constructed by intermolecular H-bonds in the crystals of 1. An S?O intermolecular contact was found in the crystals of 2, which is scarcely found for organometallic complexes. Cyclic voltammograms of 1 and 2 were studied to evaluate their redox properties. 相似文献
5.
Giuliana Gervasio Domenica Marabello Enrico Sappa Andrea Secco 《Journal of Cluster Science》2008,19(1):197-208
The thermal reactions of 2-methyl-1-hexen-3-yne [CH3CH2C≡CC(=CH2)CH3, metey] with Fe3(CO)12 have been studied: cluster opening or fragmentation and alkyne dimerization occur. Main products are the open triangular isomers [Fe3(CO)6(μ-CO)2{CH3(=CH2)CC(Et)C(Et)C(=CH2)CH3}] (complex 3a) and [Fe3(CO)6(μ-CO)2{C(Et)CCH3(=CH2)C(Et)CCH3(=CH2)}] (complex 3b). The structure and isomerism of the complexes has been confirmed by X-ray studies. The minor products of the reaction have been characterized by spectroscopic techniques. An attempt at exploiting the reactivity of the “free” C=C bonds of the coordinated ene-yne was made: complex 3a was reacted with styrene under thermal conditions. Unexpectedly considerable yields of the closed triangular cluster [Fe3(CO)6{EtC2C(=CH2)CH3}2] (complex 5) have been obtained. This behaviour had not been previously observed. The unprecedented structure of complex 5 has been confirmed with an X-ray study. 相似文献
6.
Li-Cheng Song Xiang Luo Yong-Zhen Wang Bin Gai Qing-Mei Hu 《Journal of organometallic chemistry》2009,694(1):103-10917
Treatment of parent compounds [(μ-SCH2)2X]Fe2(CO)6 (A, X = O; B, X = NBu-t; C, X = NC6H4OMe-p) with N-heterocyclic carbene IMes (IMes = 1,3-bis(mesityl)imidazol-2-ylidene) generated in situ through reaction of imidazolium salt IMes ·HCl with n-BuLi or t-BuOK afforded the monocarbene-substituted complexes [(μ-SCH2)2X]Fe2(CO)5(IMes) (1, X = O; 2, X = NBu-t; 3, X = NC6H4OMe-p). Similarly, the monocarbene and dicarbene-substituted complexes [(μ-SCH2)2NBu-t]Fe2(CO)5[I∗Mes(CH2)3I∗Mes]·HBr (4) and [(μ-SCH2)2CH2Fe2(CO)5]2[μ-I∗Mes(CH2)3I∗Mes] (5, I∗Mes = 1-(mesityl)imidazol-2-ylidene) could be prepared by reactions of parent compound B with the mono-NHC ligand-containing imidazolium salt [I∗Mes(CH2)3I∗Mes] · HBr and parent compound [(μ-SCH2)2CH2]Fe2(CO)6 (D) with di-NHC ligand I∗Mes(CH2)3I∗Mes (both NHC ligands were generated in situ from reaction of n-BuLi with imidazolium salt [I∗MesI∗Mes(CH2)3I∗Mes] · 2HBr), respectively. The imidazolium salt [I∗Mes(CH2)3I∗Mes] · 2HBr was prepared by reaction of 1-(mesityl)imidazole with Br(CH2)3Br. All the new model compounds 1-5 and imidazolium salt [I∗Mes(CH2)3I∗Mes] · 2HBr were fully characterized by elemental analysis, spectroscopy, and X-ray crystallography. On the basis of electrochemical studies of 1 and 2, compound 2 was found to be a catalyst for proton reduction to hydrogen. In addition, an EECC mechanism for this electrocatalytic reaction is preliminarily suggested. 相似文献
7.
LIU Bin ZHAO QianYi WANG HuiJuan ZENG BiRong CAO XiaoYu XIA HaiPing 《中国科学:化学(英文版)》2013,56(8):1105-1111
We studied the reactivity of an osmium vinyl complex containing a coordinated hydroxyl group OsCl2(PPh3)2[CH=C(PPh3)CHPh(OH)] (1) toward bidentate ligand 1,4-bis(diphenylphosphino)butane (DPPB),acid ligand (CO),base (Cs2CO3) and heat.Two osmium vinyl complexes OsCl2(dppb)[CH=C(PPh3)CHPh(OH)](2) and OsCl2(CO)2(PPh3)[CH=C(PPh 3)CHPh(OH)] (3),as well as two relatively rare phosphonium-containing osmafuran complexes Os(2-OCOO)(PPh3)2[CHC(PPh3)CPhO](4) and OsCl2 (PPh3)2[CHC(PPh3)CPhO](5),were obtained in high yields from these reactions.All products were characterized by NMR spectroscopy,elemental analysis,and their structures were further confirmed by single crystal X-ray diffraction. 相似文献
8.
Xu-Feng Liu 《Transition Metal Chemistry》2016,41(5):547-554
Reaction of [μ-SC6H3(CH3)S-μ]Fe2(CO)6 (1) with 2 equivalents of PPh3 gave the monosubstituted complex [μ-SC6H3(CH3)S-μ]Fe2(CO)5(PPh3) (2) plus the disubstituted [μ-SC6H3(CH3)S-μ]Fe2(CO)4(PPh3)2 (3), while the complexes [μ-SC6H3(CH3)S-μ]Fe2(CO)5[P(3-C6H4CH3)3] (4) and [μ-SC6H3(CH3)S-μ]Fe2(CO)5[P(4-C6H4F)3] (5) were prepared by the reactions of 1 with P(3-C6H4CH3)3 or P(4-C6H4F)3 in the presence of Me3NO. Complexes 3–5 were characterized by IR, NMR spectroscopy and single-crystal X-ray diffraction analysis. The molecular structures of 3–5 reveal that in each case, the phosphine ligand occupies the apical position in an overall distorted square pyramidal iron(I) complex geometry. 相似文献
9.
Two carboxy-functionalized diiron complexes [{(μ-SCH2)2X}{Fe(CO)3}{Fe(CO)2L}] (X = NC3H7, L = Ph2PCH2CH2COOH, 4; X = CH2, L = Ph2PCH2COOH, 5) were prepared, as biomimetic models of the [FeFe] hydrogenase active site, from the CO-replacement of [{(μ-SCH2)2NC3H7}Fe2(CO)6] (1) and (μ-pdt)Fe2(CO)6 (2) by phosphine ligands in CH3CN at 40 °C, respectively. In contrast, the reaction of 1 with Ph2PCH2COOH under the same condition afforded complex [{(μ-SCH2)2NC3H7}{Fe(CO)3}{Fe(CO)2(Ph2PCH3)}] (3) with a decarboxylated phosphine ligand. The molecular structures of complexes 3-5 were determined by X-ray crystallographic analyses, which show that they have similar frameworks with the phosphine ligand on the apical position. The interesting C-H···S contacts between the methylene hydrogen atoms of the PhCH2COOH ligand and the μ-S atoms of the pdt-bridge are found in the crystal of 5. According to the experimental evidence, a plausible mechanism, via sequential phosphine coordination, N-protonation, and decarboxylation steps, is proposed for the formation of 3 and for explanation of the contrastive reactivities of the adt- (2-aza-1,3-propanedithiolato) and the pdt- (1,3-propanedithiolato) bridged diiron complexes toward decarboxylation of the Ph2PCH2COOH ligand. 相似文献
10.
Heinrich Lang Bettina Lühmann Roy Buschbeck 《Journal of organometallic chemistry》2004,689(22):3598-3603
A straightforward method for the preparation of metallo carbosiloxanes of type Si(OCH2CH2CH2SiMe2[OCH2PPh2M(CO)n])4 (n = 3, M = Ni, 7a; n = 4, M = Fe, 7b; n = 5: M = Mo, 7c; M = W, 7d), Si(OCH2CH2CH2SiMe[OCH2PPh2Ni(CO)3]2)4 (8) and Me2Si(OCH2CH2CH2SiMe[OCH2PPh2Ni(CO)3]2)2 (11) is described. The reaction of Si(OCH2CH2CH2SiMeXCl)4 (1: X = Me, 2: X = Cl) or Me2Si(OCH2CH2CH2SiMeCl2)2 (9) with HOCH2PPh2 (3) produces Si(OCH2CH2CH2SiMe2(OCH2PPh2))4 (4), Si(OCH2CH2CH2SiMe(OCH2PPh2)2)4 (5) or Me2Si(OCH2CH2CH2SiMe(OCH2PPh2)2)2 (10) in presence of DABCO. Treatment of the latter molecules with Ni(CO)4 (6a), Fe2(CO)9 (6b), M(CO)5(Thf) (6c: M = Mo; 6d: M = W), respectively, gives the title compounds 7a-7d, 8 and 11 in which the PPh2 groups are datively bound to a 16-valence-electron metal carbonyl fragment.The formation of analytical pure and uniform branched and dendritic metallo carbosiloxanes is based on elemental analysis, and IR, 1H, 13C{1H}, 29Si{1H} and 31P{1H} NMR spectroscopic studies. In addition, ESI-TOF mass spectrometric studies were carried out. 相似文献
11.
Li-Cheng Song Jian-Hua Ge Xu-Feng Liu Li-Qun Zhao Qing-Mei Hu 《Journal of organometallic chemistry》2006,691(26):5701-5709
As biomimetic models for the active site of Fe-only hydrogenases,six new N-substituted diiron azadithiolates (ADT) were prepared.Treatment of CH2Cl2 solutions of primary amines RNH2 with paraformaldehyde followed by an excess of SOCl2 gave N,N-bis(chloromethyl)amines RN(CH2Cl)2 (1,R = CH2CO2Et;2,C6H4C(O)Me-p;3,C6H4CO2Me-p;4,C6H4SCN-p) in 30-90% yields.Further treatment of the chloromethylated amines 1-4 with (μ-LiS)2Fe2(CO)6 in THF resulted in formation of the corresponding N-substituted ADT-type models [(μ-SCH2)2NR]Fe2(CO)6 (5,R = CH2CO2Et;6,C6H4C(O)Me-p;7,C6H4CO2Me-p;8,C6H4SCN-p) in 24-75% yields.Also prepared were the N-substituted models [(μ-SCH2)2NC(O)CH2C10H7-α]Fe2(CO)6 (9) and 1,4-[Fe2(CO)6(μ- SCH2)2NC(O)]2C6H4 (10) by reaction of CH2Cl2 solutions of [(μ-SCH2)2NH]Fe2(CO)6 with α-C10H7CH2COCl and 1,4-C6H4(COCl)2 in 81% and 28% yields, respectively. All the new compounds 1-10 were characterized by elemental analysis and spectroscopy, as well as for 5-7 and 9 by X-ray crystallography. The crystallographic studies indicated that the functionality of 5 attached to the bridged N atom lies in an equatorial position, whereas those of functionalities of 6, 7, and 9 are located in an axial position. This is presumably due to different electronic and steric effects between the N-substituted aliphatic and aromatic functionalities. More interestingly, model 7 has been found to be a catalyst for proton reduction in the presence of either strong acid CF3CO2H or weak acid HOAc under electrochemical conditions. In addition, two mechanisms ECCE and EECC are preliminarily suggested for such two electrocatalytic H2 production processes, respectively. 相似文献
12.
Pei-Hua Zhao Sheng-Nan Liu Yun-Feng Liu Ya-Qing Liu 《Journal of Cluster Science》2014,25(5):1331-1340
As the active site models of [FeFe]-hydrogenase, two new tertiary phosphine-substituted diiron propanedithiolate complexes [(μ-PDT)Fe2(CO)5L] (PDT = SCH2CH2CH2S, L = P(PhMe-m)3, 1; PPh2(CH2CH2CH3), 2) have been prepared through carbonyl substitution reactions of parent complex [(μ-PDT)Fe2(CO)6] (A) with P(PhMe-m)3 or PPh2(CH2CH2CH3) in the presence of the decarbonylating agent Me3NO·2H2O in MeCN at room temperature. The new complexes 1 and 2 were fully characterized by elemental analysis, FT-IR, 1H, 13C{1H}, and 31P{1H} NMR spectroscopy, as well as for 1 by X-ray crystallography. In addition, the crystal structure of 1 has indicated that the phosphorus atom of the P(PhMe-m)3 ligand resides in an apical position of the pseudo-square-pyramidal geometry of the tertiary phosphine-coordinated Fe2 atom. 相似文献
13.
V. Crocq J. -C. Daran M. Gouygou B. Heim Y. Jeannin R. Speel 《Journal of Cluster Science》1996,7(4):505-529
The diiron ynamine complex [Fe2(CO)7{μ-CR)C(NEt2)}] (1:R=Me,2:R = C3H5.3:R=SiMe3.4:R = Ph) reacts at room temperature with diphenyldiazomethane Ph2CN2, in hexane to yield complexes [Fe2(CO)6{C(R)C(NEt2)N (NCPh2)] (5a:R=Me,6a:R=C3H5.7a R=SiMe3.8a:R=Ph) resulting from the insertion of the terminal nitrogen atom into the Fe=C carbene bond. Insertion the second nitrogen atom and formation of compounds [Fe2(CO)6zμ-C(R)C(NEt2)NN(CPh2)}] (5b:R=Me,6b:R=C3H5,7b:R=SiMe3,8b:R=Ph) is observed when compounds5a-5a are treated in refluxing hexane. Transformation of compoundsa tob is also obtained at room temperature within a few days. All compounds were identified by their1H NMR spectra. Compounds6a, 7a, 8a, and8b were characterized by single crystal X-ray diffraction analyses. Crystal data: for6a: space group = P21/n,a=12.853(1) A,b=24.800(7) A,c=8.947(6) A,β=99.29(3)°,Z=4, 2227 rellectionsR=0,038; for7a: space group=Pl,a=ll.483(4) A,b=14.975(4) A,c = 17.890(8) A,α = 82.80(3)°,β=94.29(7)°,γ=85.42(2),Z = 4, 5888 reflectionR = 0.035: for8a: space group = Pcab.a = 31.023(8) A.b=20.137(1) A.c=9.686(2) A.Z=8. 1651 reflections,R=0.071; for8b: space group=P21/n,a=21.459(4),b=10,100(3) A,c=28,439(8) A,ß=103.86(4)°,Z=8. 2431 reflections.R=0.057. 相似文献
14.
Fabio Carniato Giuliana Gervasio Enrico Sappa Andrea Secco 《Journal of organometallic chemistry》2009,694(26):4241-4249
The complex Co2(CO)6[μ-η2-(H3CCCCH2CH2OH)] (1) with the ligand 3-pentyn-1-ol (pol) has been synthesized following established procedures. Its structure has been determined by X-ray analysis. The complex Co2(CO)6(mbo) (mbo = 2-methyl-3-butyn-2-ol, HCCC(CH3)2OH), (3), along with the already known Co2(CO)6(bud) (bud = 1,4-butyn-diol, HOCH2CCCH2OH) (2), and Co2(CO)8 were reacted with 2(diphenylphosphino)ethyl-triethoxysilane [Ph2PCH2CH2Si(OCH2CH3)3] (dpts) and tris(hydroxymethyl)phosphine [P(CH2OH)3] (thp). With dpts, mono- and di-substituted complexes were obtained: these were characterized by analytical and spectroscopic techniques. The structures of Co2(CO)6(dpts)2 (5) and of Co2(CO)4(pol)(dpts)2 (8) have been determined by X-ray analysis.Complex (1) was reacted with 3-(triethoxysilyl)propyl isocyanate [(H3CCH2O)3Si(CH2)3NCO] (tsi): the new complex Co2(CO)6[H3CCCCH2CH2OC(O)NH(CH2)3Si(OCH2CH3)3] (9) was obtained and spectroscopically characterized. The complex has also been reacted with tetraethyl orthosilicate (teos); a new inorganic-organometallic material was obtained. Complex (5) has been grafted on the mesoporous material SBA-15. The hybrid inorganic-organometallic materials obtained have been characterized by inductively coupled plasma-mass spectrometry (ICP-MS), infrared spectroscopy (FT-IR) under vacuum conditions, X-ray diffraction (XRD) and scanning electron microscopy coupled to EDS probe (SEM-EDS). 相似文献
15.
N. S. Emelyanova A. F. Shestakov I. V. Sulimenkov T. N. Rudneva N. A. Sanina S. M. Aldoshin 《Russian Chemical Bulletin》2012,61(1):1-11
Decomposition products of [Fe2S2(CH2CH2NH3)2(NO)4]SO4·2.5H2O (1??) were studied by electrochemistry and mass spectrometry. The structures of the dicationic tetranitrosyl iron complex with cysteamine of the composition [Fe2S2(CH2CH2NH3)2(NO)4]2+ (1) and possible products of its decomposition and NO replacement by an aqua ligand were studied by quantum chemical methods at the density functional theory level. Taking into account the solvation effects, the replacement of the nitrosyl ligand in dication 1 by an aqua ligand was found to be less favorable in aqueous solution than in the gas phase. The pK value was calculated for the proton abstraction from the NH3 group of compound 1 (7.2), and the removal of NO from the deprotonated form of the complex was found to be much easier. This result is consistent with the experimental data on an increase in the rate of NO formation in aqueous solutions of 1 with increasing pH from 6 to 8 assuming that the increase in pH is accompanied by an increase in the percentage of the less stable deprotonated form of the complex and that OH? does not participate in the elementary step of NO formation. The kinetic curves of NO formation are well described by a two-step scheme of consecutive first-order reactions of the NO formation and consumption. In the gas phase, dication 1 was found to be unstable to decomposition into two mononuclear cationic dinitrosyl iron complexes with cysteamine. This result is consistent with the fact that these cations are observed in the electrospray ionization mass spectrometric experiment. The major peak in the mass spectra is associated with the [Fe2S2(CH2CH2NH3)2(NO)4 ? H]+ ion. As follows from the calculations, this is due to the deprotonation of the dication as it gets rid of the hydration shell, because even the dimer of water molecules is more basic than dication 1. 相似文献
16.
S. T. Orlova T. A. Stromnova D. N. Kazyul"kin L. I. Boganova D. I. Kochubey B. N. Novgorodov 《Russian Chemical Bulletin》2004,53(4):819-824
The reaction of tetranuclear Pd4(μ-COOCH3)4(μ-CO)4 cluster (1a) with p- and o-chloronitrosobenzenes was found to give dinuclear nitrosoamide complexes, Pd2(OAc)2(p-ClC6H4N[p-ClC6H3NO])2 (4) and Pd2(OAc)2(o-ClC6H4N[o-ClC6H3NO])2 (5), respectively. The formation of complexes 4 and 5 is accompanied by evolution of CO2, resulting from oxidation of CO coordinated in cluster 1. Complexes 4 and 5 were characterized by elemental analysis and IR and 1H NMR spectroscopy; their structures were studied by EXAFS. The reactions of dinuclear complex 4 with molecular hydrogen and CO were studied. The major products of reduction of 4 with hydrogen include metallic palladium, acetic acid, cyclohexanone, and molecular nitrogen. Treatment of complex 4 with CO under mild conditions (1 atm, 20 °C) affords p-chlorophenyl isocyanate. 相似文献
17.
The core structure (μ-SCH2)2NH[Fe2(CO)6] (5) of Fe-only hydrogenases active site model has been synthesized by the condensation of iron carbonyl sulfides, formaldehyde and silyl protected amine. Its monosubstituted complexes (μ-SCH2)2NH[Fe2(CO)5PR3] (R = Ph (6), Me (7)) were accordingly prepared. The coordination configurations of 5 and 6 were characterized by X-ray crystallography. Protonation of complex 7 to form the N-protonated product occurs in an acetonitrile solution upon addition of triflic acid. The redox properties of these model complexes were studied by cyclic voltammetry. 相似文献
18.
The first bidentate phosphanylborohydride: Synthesis, structure, and reactivity towards [CpFe(CO)2I]
Franz Dornhaus 《Journal of organometallic chemistry》2007,692(14):2949-2955
Deprotonation of the phosphane-borane adduct rac/meso-(HP(BH3)(Ph)CH2)2 (2) with KH provides facile access to the bidentate phosphanylborohydride rac/meso-K2[(P(BH3)(Ph)CH2)2] (3). Treatment of 3 with two equivalents of [CpFe(CO)2I] gives the dinuclear complex rac/meso-[(CpFe(CO)2)2-μ-(P(BH3)(Ph)CH2)2] (4). Single crystals of the pure diastereomers meso-2, meso-3(thf)4, and rac-4 have been grown from toluene/pentane, diethyl ether/thf, and benzene/pentane, respectively. The molecular structures of all three compounds have been determined by X-ray crystallography. 相似文献
19.
Reaction of the parent complex (μ-PDT)Fe2-(CO)6 (A) (PDT = 1,3-SCH2CH2CH2S2?) with the bidentate N/P ligand [(Ph2P)2N(C6H4Cl-p)] in the presence of Me3NO as decarbonylating agent produced an unexpected iron–sulfur complex [(μ-PDT)Fe2(CO)5{PPh2(NHC6H4Cl-1,4)}] (1). Extending this chemistry further, two similar complexes [(μ-PDT)Fe2(CO)5{PPh2(NHC6H4NO2-1,4)}] (2) and [(μ-PDT)Fe2(CO)5{PPh2(NHC6H4CO2Et-1,4)}] (3) could be prepared from the simple substitution reactions of the precursor A with the monodentate N/P ligands Ph2P(NHC6H4NO2-1,4) and Ph2P(NHC6H4CO2Et-1,4), respectively. These new complexes, which can be considered as active site models of [FeFe] hydrogenases, have been characterized by elemental analysis, FTIR, and NMR (1H, 13C, 31P) spectroscopies, as well as by X-ray crystallography for complex 1. 相似文献
20.
Three new monophosphine-substituted iron carbonyl cluster complexes [(μ-PDT)Fe2(CO)5L] [(PDT = SCH2CH2CH2S, L = P(CH2Ph)3, 1; P(C6H11)3, 2; PPh2(PhMe-p), 3)], which can be regarded as active site mimics for [FeFe]-hydrogenase, have been prepared in 40–70 % yields by reactions of the parent complex (μ-PDT)Fe2(CO)6 (A) with monophosphine ligands in the presence of the decarbonylating agent Me3NO·2H2O. All three complexes were characterized by elemental analysis and spectroscopic techniques, as well as by X-ray crystallography for complex 1. The IR spectra of the complexes reveal that the electron-donating abilities of the different monophosphine ligands follow the order PPh2(PhMe-p) > P(C6H11)3 > P(CH2Ph)3. 相似文献