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1.
利用Co 2(CO) 8与[Cl 3CC(O)OCH 2] 2的反应合成了以C(O)OCH 2CH 2OC(O)桥联两个Co 3C四面体骨架为特征的新型双四面体簇合物[(CO) 9Co 3(μ 3-C)C(O)OCH 2] 2(1);1与不同物质的量比的Na[M(CO) 3C 5H 4R](M=Mo,W;R=H,C(O)Me)反应,得到一步交换的产物(CO) 9Co 3(μ 3-C)C(O)OCH 2CH 2OC(O)(μ 3-C)Co 2M(CO) 8(C 5H 4R)[M=Mo,R=H(2);M=Mo,R=C(O)Me(3);M=W,R=H(4);M=W,R=C(O)Me(5)]或两步交换的产物[(C 5H 4R)(CO) 8Co 2M(μ 3-C)C(O)OCH 2] 2[M=Mo,R=H(6);M=Mo,R=C(O)Me(7);M=W,R=H(8);M=W,R=C(O)Me(9)].5或9分别与Na[Mo(CO) 3C 5H 5]以12的物质的量比反应得到含一个手性四面体骨架(CoMoWC)的(C 5H 5)(CO) 8Co 2Mo(μ 3-C)C(O)OCH 2CH 2O·C(O)(μ 3-C)CoMoW(CO) 7(C 5H 4C(O)Me)(C 5H 5)(10)或含两个手性四面体骨架(CoMoWC)的[(C 5H 5)(C 5H 4C(O)Me)(CO) 7CoMoW(μ 3-C)C(O)OCH 2] 2(11);对化合物1_11进行了CH元素分析、IR和 1HNMR等表征.结果表明,在金属交换反应中处于不同簇环境下的Co(CO) 3基团反应活性不同.对化合物1进行了晶体X射线衍射分析.化合物1的晶体属单斜晶系,P2 1/n(#14)空间群,晶胞参数a=0.933 0(2)nm,b=1.519 7(4)nm,c=1.178 3(4)nm,=91.16(2)°,Z=2,F(000)=972.分子结构呈中心对称. 相似文献
2.
[Ru 3(CO) 12]与Lawesson试剂[(MeOC 6H 4PS 2) 2]反应,合成、分离并用谱学表征了产物三核钌羰合簇[(μ-H) 2Ru 3(CO) 9(μ 3-P)](Ⅰ)和四核钌羰合簇[(Ru 4(CO) 10(μ 3-S)(μ 3-PC 6H 4OMe)](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Ru 4簇心,其三角形面上分别具有面桥基μ 3-S和μ 3-PC 6H 4OMe基配体. 相似文献
3.
在Fe(CO) 5+[Et 4N] 2MoS 4相同体系中,改变原料配比及碱度,可得到3种簇合物:(Ⅰ)[Et 4N] 2[Fe 2(CO) 8]、(Ⅱ)[Et 4N] 2[Fe 3S(CO) 9]、(Ⅲ)[Et 4N] 3[FeMo 2S 8O 2]。本文用电子光谱法考察了各簇合物的生成条件。根据X光结构分析,用群分解的EHMO程序,计算了(Ⅰ)、(Ⅱ)簇合物阴离子骨架能级,并研究了它们的电子光谱及电子结构。 相似文献
4.
Reaction of ferrocenoyl chloride with [Et_3NH] [(μ-CO)(μ-RS) Fe_3=(CO)_(?)] complexes gave bridging ferrocenoyl complexes(μ-FcCO)(μ-RS)Fe_(?)(CO)_(?) (Fc=ferrocenyl, R=Et, i-Pr, n-Bu, t-Bu, Ph).The structures of all new complexes were characterised by ~1HNMR, IR and MS. 相似文献
5.
具有五元环结构的偶氮化合物4,4-二甲基-4,5-二氢-3 H-吡咯(N 2C 5H 10),与Fe 3(CO) 12在甲苯中加热回流反应,生成双铁六羰基配合物Fe 2(N 2C 5H 10)(CO) 6(1).反应中N=N双键被还原,配体以(N 2C 5H 10) 2-的形式与Fe IFe I配位,形成具有蝶形结构的34e -化合物.研究了在脱羰基试剂Me 3NO存在条件下,1和单齿膦配体PR 3反应生成Fe 2(N 2C 5H 10)-(CO) 5(PR 3)(PR 3=PPh 3,2a;PCy 3,2b)单取代配合物.光照条件下,化合物1中的CO配体还可以被双齿膦配体dppe[dppe=1,2-C 2H 4(PPh 2) 2]和dppbz[dppbz=1,2-C 6H 4(PPh 2) 2]取代,生成产物的类型和膦配体的夹角相关.与夹角较大的dppe反应,生成桥连产物Fe 2(N 2C 5H 10)(CO) 4( μ-dppe)(3a);而与刚性较大的dppbz反应时,Fe 2(NR) 2的蝶形结构打开呈四元环;其中一个Fe上的CO被取代,dppbz与该Fe中心螯合,生成具有桥连CO的化合物Fe 2(N 2C 5H 10)( μ-CO)(CO) 4( κ2-dppbz)(3b).合成具有Fe I-CO-Fe I结构的羰基化合物,一直是模拟[FeFe]氢化酶活性中心还原态结构Fe 2(SR) 2( μ-CO)-(CO) 5-xL x的重要挑战.该类Fe 2(NR) 2(CO) 6-x(PR 3) x化合物的合成,能为探索模拟[FeFe]氢化酶活性中心结构提供新的途径和思路.以上化合物均通过核磁[ 31P( 1H)NMR]、红外光谱(IR)、元素分析及X射线单晶结构衍射等表征. 相似文献
6.
利用(μ 3-CCO 2Et)Co 3(CO) 9与单阴离子试剂[Mo(CO) 3(η 5-C 5H 4R)]-[R=H,C(O)Me]的反应合成了2个新的含CCo 2Mo骨架的簇合物(μ 3-CCO 2Et)Co 2Mo(CO) 8(η 5-C 5H 4R)[R=H(1);R=C(O)Me(2)],进而用其与双阴离子试剂{-M(CO) 3[η 5-C 5H 4C(O)]} 2-1,4-C 6H 4[M=Mo,W]反应合成了4个双四面体簇合物{(μ 3-CCO 2Et)CoMoM(CO) 7(η 5-C 5H 4R)[η 5-C 5H 4C(O)]} 2-1,4-C 6H 4[M=Mo,R=H(3);M=Mo,R=C(O)Me(4);M=W,R=H(5);M=W,R=C(O)Me(6)].这6个化合物的C和H元素分析,IR, 1HNMR等表征都与其结构一致.晶体X射线衍射分析表明,化合物2属单斜晶系,C 2/c空间群,晶胞参数a=1.1264(3)nm,b=1.1879(3)nm,c=3.3565(10)nm,β=93.320(5)°,V=4.484(2)nm 3,Z=8,D c=1.867g·cm -3,F(000)=2480,R=0.0369,wR=0.1150. 相似文献
7.
C 2H 5SPCl 2与Co 2(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CO 7(μ 7-S)(μ 4-PSC 2H 5)(μ-SC 2H 5) 2(μ-CO) 2(CO) 12,是八面体骨架Co 4PS和四面体骨架Co 3S结合的松散原子簇合物。 相似文献
8.
测定了(p-CH 3OC 6H 4) 2TeO存在下M 2(CO) 10(M=Mn,Re)的CO取代反应速率及活化参数。其表观速率常数分别与M 2(CO) 10和(p-CH 3OC 6H 4) 2TeO的浓度的一次方成正比。本文所建议的缔合机理与前人用(CH 3) 3NO作氧原子转移试剂的相应反应所提出的机理相似。讨论了在(CH 3) 3NO和(p-CH 3OC 6H 4) 2TeO存在下影响M 2(CO) 10的CO取代反应速率的因素。 相似文献
9.
碳锗双桥连二环戊二烯(Me 2C)(Me 2Ge)(C 5H 4) 2(1)与五羰基铁在回流甲苯及二甲苯中的反应,得到正常的Fe-Fe键化合物(Me 2C)(Me 2Ge)[(η 5-C 5H 3)Fe(CO)] 2(μ-CO) 2(3)和脱锗桥产物(Me 2C)[(η 5-C 5H 4)Fe(CO)] 2(μ-CO) 2(4)以及一个结构新颖的化合物(Me 2C)[(η 5-C 5H 3)[(Me 2Ge)Fe(CO) 2](η 1,η 5-C 5H 3)[Fe(CO) 2](2).用X射线衍射分析測定了化合物3的晶体结构,并提出了可能的生成机理. 相似文献
10.
用Co 2(CO) 8与有机杂环二硫代次膦酸盐SP(C 6H 4OR)(S)N(C 6H 5)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Co 4(CO) 10(μ 4-S)[μ 4-P(C 6H 4OR)](1:R=Me;3:R=Et)和Co 4(CO) 10(μ 3-S)[μ 2-P(C 6H 4OR)N(C 6H 5)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,P2 1/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)nm 3,Z=4,D c=1.743g/cm 3.Co1Co3Co4呈三角形分布,其中Co-Co平均键长为0.251nm,而Co 2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. 相似文献
11.
Through reductive reaction between PhL1 and μ-S2 Fe (CO/6,tollowed by nucleophilicsubstitution of the intermediate (μ-PhS} (μ-LIS} Fe2 (CO)6 toward RX,nine Fe-S clus-ter complexes of (μ-PhS)(μ-RS)Fe2(CO)6 series have been synthesized.The influence of RX structures on the activities in nucleophilic substitution has been examined and possible steroisomers and isomer ratios of the complexes determined.In addition,the regular variations of isomer's CH3-S and CH2-S which are caused by the anisotropic effects of C-O and orientations of unshared electron pairs on sulfurs,have also been preliminarily discussed. 相似文献
12.
Fourteen new PPh3 substituted Fe-S clusters,with general formula (μ-RS)(μ-R'S)Fe2(CO)5 PPh3,have been synthesized by reaction of unsymmetrical type of bis(μ-alkylthio ) hexacarbonyldiirons with triphenylphosphine.Based on the discussion of influence of PPh3 on VCO and alkyl spacial orientation of PPh3 in clusters has also been established. 相似文献
13.
The compounds (π-C 5H 5)(CO) 2LM-X (L = CO, PR 3; M = Mo, W; X = BF 4, PF 6, AsF 6, SbF 6) react with H 2S, p-MeC 6H 4SH, Ph 2S and Ph 2SO(L′) to give ionic complexes [(π-C 5H 5)(CO) 2LML′] + X −. Also sulfur-bridged complexes, [(π-C 5H 5)(CO) 3W---SH---W(CO) 3(π-C 5H 5)] + AsF 6− and [(π-C 5H 5)(CO) 3M-μ-S 2C=NCH 2Ph-M(CO) 3(π-C 5H 5)], have been obtained. Reactions with SO 2 and CS 2 have been examined. 相似文献
14.
A high yield synthesis of the carbonyl dithiocarbamato derivative Fe(CO) 2(η 2-S 2CNMe 2) 2 and Fe(η 2-S 2CNMe 2) 2 by photolysis with visible light of solutions containing Fe 2(CO) 9 or Fe 3(CO) 12 and [(η 5-C 5H 5)(CO) 3W(η 1-SCSNMe 2)] is reported. 相似文献
15.
Reductive dehalogenation of the (chloro)(phenylethynyl)phosphine (2,4,6- tBu 3C 6H 2O)(PhCC)PCl, I, by Co 2(CO) 8, II, yields the neutral phosphenium ion complex [(R)(R′)]P=Co(CO) 3, III, (R = 2,4,6- tBu 3C 6H 2O; R′ = (η 2-C≡CPh)Co 2(CO) 6), which contains a trigonally planar coordinated phosphorus atom. When NaCo(CO) 4, V, is used instead of II a dinuclear complex, Co 2(CO) 6[μ 2-P(R)(R′)] 2, VI, (R = 2,4,6- tBu 3C 6H 2O; R′ = C≡CPh) is formed in which the phosphido ligands P(R)(R′), bridge in a μ 2 fashion two Co(CO) 3 units. The mechanism of formation of VI, involving a formal dimerization of two [(2,4,6- tBu 3C 6H 2O)(PhC≡C)]P=Co(CO) 3 fragments, is discussed. However, ( tBu)(PhC≡C)PCl, VII, reacts with II, to yield the cluster compound VIII, containing the two μ 2-bridging units ( tBu)[(η 2-C≡CPh)Co 2(CO) 5]P and ( tBu)(PhC≡C)P. Compounds II and VI–VIII were identified from their analytical and spectroscopic (IR, 1H-, 13C- and 31P-NMR) data. The molecular structure of the cluster compound VIII was determined by an X-ray diffraction study. 相似文献
16.
The preparation and properties as well as some reactions of a series of arylcarbonylbis(triphenylphosphine)iridium(I) complexes [Ir(Ar)(CO)(PPh 3) 2] (Ar = C 6H 5, C 6F 5, 2-C 6H 4CH 3, 3-C 6H 4CH 3, 4-C 6H 4CH 3, 2-C 6H 4OCH 3, 2,6-C 6H 3-(OCH 3) 2, 4-C 6H 4N(CH 3) 2, 3-C 6H 4Cl, 4-C 6H 4Cl, 4-C 6H 4Cl, 3-C 6H 4CF 3, 4-C 6H 4CF 3) are described, and the most important IR data as well as the 31P NMR parameters of these, without exception trans-planar, compounds are given. Some of the complexes react with molecular oxygen to form well defined dioxygen adducts [Ir(Ar)(O2)(CO)(PPh3)2] (Ar = C6H5, 3-C6H4CH3, 4-C6H4CH3). Complexes with ortho-substituted aryl ligands are not oxygenated. This effect is referred to as a steric shielding of the metal center by the corresponding ortho-substituents. With SO2 the similar irreversible addition compound [Ir(4-C6H4CH3)-(SO2)(CO)(PPh3)2] is obtained. Sulfur dioxide insertion into the Ir---C bond cannot be observed. The first step of the reaction between [Ir(4-C6H4CH3)(CO)(PPh3)2] and hydrogen chloride involves an oxidative addition of HCl to give [Ir(H)(Cl)(4-C6-H4CH3)(CO)(PPh3)2]. Ir---C bond cleavage by reductive elimination of toluene from the primary adduct does not occur except at elevated temperature. 相似文献
17.
The reaction of the anionic mononuclear rhodium complex [Rh(C 6F 5) 3Cl(Hpz)] t- (Hpz = pyrazole, C 3H 4N 2) with methoxo or acetylacetonate complexes of Rh or Ir led to the heterodinuclear anionic compounds [(C 6F 5) 3Rh(μ-Cl)(μ-pz)M(L 2)] [M = Rh, L 2 = cyclo-octa-1,5-diene, COD (1), tetrafluorobenzobarrelene, TFB (2) or (CO) 2 (4); M = Ir, L 2 = COD (3)]. The complex [Rh(C 6F 5) 3(Hbim)] − (5) has been prepared by treating [Rh(C 6F 5) 3(acac)] − with H 2bim (acac = acetylacetonate; H 2bim = 2,2′-biimidazole). Complex 5 also reacts with Rh or Ir methoxo, or with Pd acetylacetonate, complexes affording the heterodinuclear complexes [(C 6F 5) 3Rh(μ-bim)M(L 2)] − [M = Rh, L 2 = COD (6) or TFB (7); M = Ir, L 2 = COD (8); M = Pd, L 2 = η 3-C 3H 5 (9)]. With [Rh(acac)(CO) 2], complex 5 yields the tetranuclear complex [{(C 6F 5) 3Rh(μ-bim)Rh(CO) 2} 2] 2−. Homodinuclear Rh III derivatives [{Rh(C 6F 5) 3} 2(μ-L) 2] ·- [L 2 = OH, pz (11); OH, S tBu (12); OH, SPh (13); bim (14)] have been obtained by substitution of one or both hydroxo groups of the dianion [{Rh(C 6F 5) 3(μ-OH)} 2] 2− by the corresponding ligands. The reaction of [Rh(C 6F 5) 3(Et 2O) x] with [PdX 2(COD)] produces neutral heterodinuclear compounds [(C 6F 5) 3Rh(μ-X) 2Pd(COD)] [X = Cl (15); Br (16)]. The anionic complexes 1–14 have been isolated as the benzyltriphenylphosphonium (PBzPh 3+) salts. 相似文献
18.
Three families of heterobimetallic compounds were obtained by reaction of [Mo(CO) 3(CH 3CN) 2(Cl)(SnRCl 2)] (R = Ph, Me) with P(4-XC 6H 4) 3 (X = Cl, F, H, Me, MeO). The type of compound obtained dependent on the solvent and concentration of the starting compound. So, [Mo(CO) 2(CH 3COCH 3) 2(PPh 3)(Cl)(SnRCl 2)]· nCH 3COCH 3 (R = Ph, n = 0.5; R = Me, n = 1) (type I) and [Mo(CO) 3{P(4-XC 6H 4) 3}(μ-Cl)(SnRCl 2)] 2 (R = Ph, X = Cl, F, H, Me, MeO; R = Me, X = Cl, F) (type II) were isolated from acetone solution in ca 0.05 M and 0.1 M concentrations, respectively. However, [Mo(CO) 3(CH 3CN) {P(4-XC 6H 4) 3}(Cl)(SnRCl 2)] (R = Ph, X = H; R = Me, X = Cl, F, H) (type III) were obtained from dichloromethane solution independently of the concentration used. All new complexes showed a seven-coordinate environment at molybdenum, containing Mo---Cl and Mo---Sn bonds. Mössbauer spectra indicated a four-coordination at tin for type III complexes. 相似文献
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