铁铂硫原子簇化合物的合成与结构研究 V: [MoFe3S4]类立方烷簇合物的转化反应和[Et4N]3[Mo2Fe6S8(SC6H4CH3-m)3Cl6]的晶体结构

具[MoFe2S4]类立方烷结构单元的双类立方烷化合物[Et4N]4[Mo2Fe7S8(SR)12](1a,R=Ph; 1b, R=tolyl-m)或单类立方烷化合物[MoFe3S4(dteR2)5](2a, R=Me; 2b, R=Et)与酰氯在乙腈中反应, 分别得到不含Fe桥的双类立方烷化合物(Et4N)3[Mo2Fe6S8(SR)3Cl6](3a, R=Ph; 3b, R=toly-m)与[MoFe3S4]骨架支解后的Fe(dteR2)2Cl(4a, R=Me; 4b, R=Et)。说明在相同反应条件下, [MoFe3S4]单元在1中比在2中稳定, 本文首次将1型与3型结构通过一步化学反应连系起来。3型化合物的产生得到X射线衍射测定及^1H NMR谱的证实。本文报道3b的单晶结构及3的^!H NMR数据, 3b属六方晶系, P63/m, a=1.6827(3), c=1.5951(16)nm; V=3.91158nm^3; Dc=1.491g/cm^3;Z=2; F(000)=1780; 偏离因子R=0.048, 化合物2与酰氯反应产生4, 由红外及紫外可见光谱证实。     

铁铂硫原子簇化合物的合成与结构研究 V: [MoFe3S4]类立方烷簇合物的转化反应和[Et4N]3[Mo2Fe6S8(SC6H4CH3-m)3Cl6]的晶体结构

具[MoFe2S4]类立方烷结构单元的双类立方烷化合物[Et4N]4[Mo2Fe7S8(SR)12](1a,R=Ph; 1b, R=tolyl-m)或单类立方烷化合物[MoFe3S4(dteR2)5](2a, R=Me; 2b, R=Et)与酰氯在乙腈中反应, 分别得到不含Fe桥的双类立方烷化合物(Et4N)3[Mo2Fe6S8(SR)3Cl6](3a, R=Ph; 3b, R=toly-m)与[MoFe3S4]骨架支解后的Fe(dteR2)2Cl(4a, R=Me; 4b, R=Et)。说明在相同反应条件下, [MoFe3S4]单元在1中比在2中稳定, 本文首次将1型与3型结构通过一步化学反应连系起来。3型化合物的产生得到X射线衍射测定及^1H NMR谱的证实。本文报道3b的单晶结构及3的^!H NMR数据, 3b属六方晶系, P63/m, a=1.6827(3), c=1.5951(16)nm; V=3.91158nm^3; Dc=1.491g/cm^3;Z=2; F(000)=1780; 偏离因子R=0.048, 化合物2与酰氯反应产生4, 由红外及紫外可见光谱证实。     

钼铁硫原子簇化合物的合成与结构化学IV: 双类立方烷化合物与酰氯的反应

报导了双类立方烷簇状化合物(Et4N)4[Mo2Fe7S8(SC6H5)12]与乙酰氯在乙腈中的反应, 结果获得不含Fe(SC6H5)3桥的双类立方烷化合物(Et4N)4[Mo2Fe6S8(SC6H5)9]. 反应用^1H NMR和元素分析表征. 这种类型的结构转换为首次所见, 从而对化合物中桥的松散结构提供了新的实验证据.     

含环烷巯基配体的Fe_4S_4类立方烷簇合物的合成和结构表征

报道了 2个含烷巯基配体的Fe4S4类立方烷簇合物 ,它们在氯化亚铁 ,四硫代金属酸盐及环烷硫醇组成的反应体系中生成 ,化合物的结构参数分别为 :[PhCH2 NMe3 ]2 [Fe4S4(SC5 H9) 4](Ⅰ ) ,属单斜晶系 ,空间群P2 1/c,a =1 .6 32 7( 4)nm ,b=1 .1 2 2 9( 3)nm ,c=2 .80 2 5 ( 1 0 )nm ,β =94.6 3( 2 )°,Z =4,R =0 .0 74;(Et4N) 2 [Fe4S4(SC6H11) 4](Ⅱ ) ,,属四方晶系 ,空间群I42m ,a=1 .1 6 70 5 ( 9)nm ,b=1 .1 6 70 6 ( 2 )nm ,c=2 .0 6 32 6 ( 5 )nm ,Z =2 ,Dcalc=1 .2 7g/cm3 ,R =0 .0 78.环烷巯基配体的引入没有引起Fe4S4核心结构的明显变化 ,同时讨论了阳离子对Fe4S4簇阴离子结构对称性的影响     

铁钼硫原子簇化合物的合成与结构研究 Ⅴ.[MoFe_3S_4]类立方烷簇合物的转化反应和[Et_4N]_3[Mo_2Fe_6S_8(SC_6H_4CH_(3-m))_3Cl_6]的晶体结构

具[MoFe_3S_4]类立方烷结构单元的双类立方烷化合物[Et_4N]_4[Mo_2Fe_7S_8(SR)_(12)](1a,R=Ph;1b,R=tolyl-m)或单类立方烷化合物[MoFe_3S_4(dtcR_2)_5](2a,R=Me;2b,R=Et)与酰氯在乙腈中反应,分别得到不含Fe桥的双类立方烷化合物(Et_4N)_3[Mo_2Fe_6S_8(SR)_3Cl_6](3a,R=Ph;3b,R=tolyl-m)与[MoFe_3S_4]骨架支解后的Fe(dtcR_2)_2Cl(4a,R=Me;4b,R=Et)。说明在相同反应条件下,[MoFe_3S_4]单元在1中比在2中稳定。本文首次将1型与3型结构通过一步化学反应连系起来。3型化合物的产生得到X射线衍射测定及~1H NMR谱的证实。本文报道3b的单晶结构及3的~1H NMR数据。3b属六方晶系,P6_3/m,a=1.6827(3),c=1.5951(16)nm;V=3.91158nm~3;D_c=1.491g/cm~3;Z=2;F(000)=1780;偏离因子R=0.048。化合物2与酰氯反应产生4,由红外及紫外可见光谱证实。     

[(C2H5)4N]2{Fe4S4[S2CN(C2H5)2]4}的晶体和分子结构

[(C2H5)4N]2{Fe4S4[S2CN(C2H5)2]4}单晶样品在Nicolet-R3四圆衍射仪上收集X射线衍射数据. 分析结果给出其晶胞参数: a=22.125(6), b=11.313(3),c=25.053A; β=118.05(2)°; V=5534.19A^3, Z=4, 空间群Cc. 衍射数据经过Lρ因子和经验吸收效应校正. 分子中铁原子的位置从三维Patterson图上得到. 接着经过若干轮Fourier和差Fourier电子云密度合成, 发现全部其余非氢原子的坐标.氢原子位置根据理论模型计算. 结构修正最后收敛至R=0.073, Rw=0.069. 标题化合物是由[(C2H5)4N]^+和{FeS4[S2CN(C2H5)2]}^2^-组成的离子型化合物. 结构的主要特点表现在阴离子上, 而在阴离子中含有类立方烷型簇核Fe4S4. 该簇核中每个铁原子与五个硫原子配位, 其配位多面体构型均为畸变的四方锥.     

三维多立方烷类氯桥连的Cu（Ⅱ）簇合物[Cu3Cl6]∞的水热合成及其晶体结构

立方烷结构的过渡金属簇具有特殊的磁性,催化活性和稳定性等而备受关注[1]。超过7核的立方烷类铜簇化合物已知的甚少,典型的代表有羟基氧桥连的共角二联立方烷类七核铜簇[Cu7(OH)6Cl2(pn)(H2O)2](C(CN)3)4Cl2(pn=1,3 di aminopropane)[2]和[Cu7(bpym)6(OH)8(H2O)2](NO3)6·H2O(bpym=2,2 bipyrimidine)[3]以及烷氧桥连的双立方烷类八核铜簇[Cu8L8(O2CMe)4][ClO4]4(L=di 2 pyridyldetone)[4]等。我们采用水热方法合成了多立方烷类三维的具有开放式骨架的[Cu3Cl6]∞铜簇合物,并用X射线晶体衍射进行了结构表征。1　实验部分1 1…     

过渡金属μ3-E立方烷簇合物(η ^5-C5H5)4Fe4(μ3-Se)4及 (η ^5-RC5H4) 4Cr4(μ3-S)4的合成与表征

通过 (η5 C5H5) 2 Fe2 (CO) 4和硒粉在沸腾的甲苯中反应可制得含 μ3 Se的立方烷簇合物 (η5 C5H5) 4Fe4 (μ3 Se) 4(1) ,而由 (η5 RC5H4 ) 2 Cr2 (CO) 4S在甲苯中回流可制得含 μ3 S的立方烷簇合物 (η5 RC5H4 ) 4Cr4 (μ3 S) 4(2 ,R =COMe ;3,R =CO2 Me)。企图通过 (η5 EtO2 CC5H4 ) 2 Fe2 (CO) 4(5 )和硫黄制备 μ3 S立方烷簇合物 (η5 EtO2 CC5H4 ) 4Fe4 (μ3 S) 4(6 )未获成功 ,其中 5是由 η5 EtO2 CC5H4 Fe(CO) 2 Na与 η5 EtO2 CC5H4 Fe(CO) 2 I (4 )缩合制得。新化合物 1～ 5经元素分析 ,IR和1 HNMR光谱表征     

钼铁硫原子簇化合物的合成与结构化学研究II: 以Fe(SR)6为桥的双类立方烷化合物的合成及(Et4N)4[Mo2Fe7S8(SC6H4CH3-m)12].2THF的晶体结构

在乙腈溶液中(Et4N)2[Fe4(SR)10]与(Et4N)2[MoS4]反应半小时生成对氧极为敏感的系列黑色晶状化合物(Et4N)4[Mo2Fe7S8(SR)12](R=C6H5,1;R=C6H4CH3-m, 2;R=C6H4CH3-o, 3;R=C6H4CH3-ρ,4). 2.2THF晶体的分子量为2982.8, 属单斜晶系;空间群为P21/n; a=18.022(2), b=18.375(2), c=22.254(3)A; β=71.04(1)°;V=6969(2)A^3;Dc=1.424g.cm^-^3;Z=2;F(000)=3108.晶体结构用直接法解出,修正至R=0.064. 2.2THF中Mo...Mo'距离为7.234A.     

钼(钨)/铜/硫三核簇合物[A]2[MS4(CuCN)2] (M=Mo,W;A=Et4N,PPh4)的合成及晶体结构

合成了四个三核簇合物[A]2[MS4(CuCN)2](1A＝Et4N,M＝Mo;2A＝PPh4,M＝W;3A＝Et4N,M＝W;4A＝PPh4,M＝Mo),测定了[Et4N]2[MoS4(CuCN)2]*H2O(1*H2O)和[PPh4]2[WS4(CuCN)2]*0.5DMF*H2O(2*0.5DMF*H2O)的晶体结构.1和2的簇阴离子[MS4(CuCN)2]2-(M＝Mo,W)均具有一个双齿配体MS42-和两个CuCN形成的近似D2d对称性结构.     

Selenium as a structural surrogate of sulfur: template-assisted assembly of five types of tungsten-iron-sulfur/selenium clusters and the structural fate of chalcogenide reactants

Syntheses of five types of tungsten-iron-sulfur/selenium clusters, namely, incomplete cubanes, single cubanes, edge-bridged double cubanes (EBDCs), P(N)-type clusters, and double-cuboidal clusters, have been devised using the concept of template-assisted assembly. The template reactant is six-coordinate [(Tp*)W(VI)S(3)](1-) [Tp* = tris(3,5-dimethylpyrazolyl)hydroborate(1-)], which in the assembly systems organizes Fe(2+/3+) and sulfide/selenide into cuboidal [(Tp*)WFe(2)S(3)] or cubane [(Tp*)WFe(3)S(3)Q] (Q = S, Se) units. With appropriate terminal iron ligation, these units are capable of independent existence or may be transformed into higher-nuclearity species. Selenide is used as a surrogate for sulfide in cluster assembly in order to determine by X-ray structures the position occupied by an external chalcogenide nucleophile or an internal chalcogenide atom in the product clusters. Specific incorporation of selenide is demonstrated by the formation of [WFe(3)S(3)Se](2+/3+) cubane cores. Reductive dimerization of the cubane leads to the EBDC core [W(2)Fe(6)S(6)Se(2)](2+) containing μ(4)-Se sites. Reaction of these species with HSe(-) affords the P(N)-type cores [W(2)Fe(6)S(6)Se(3)](1+), in which selenide occupies μ(6)-Se and μ(2)-Se sites. The reaction of [(Tp*)WS(3)](1-), FeCl(2), and Na(2)Se yields the double-cuboidal [W(2)Fe(4)S(6)Se(3)](2+/0) core with μ(2)-Se and μ(4)-Se bridges. It is highly probable that in analogous sulfide-only assembly systems, external and internal sulfide reactants occupy corresponding positions in the cluster products. The results further demonstrate the viability of template-assisted cluster synthesis inasmuch as the reduced (Tp*)WS(3) unit is present in all of the clusters. Structures, zero-field M?ssbauer data, and redox potentials are presented for each cluster type.     

SYNTHESIS AND STRUCTURE OF THE FIRST TUNGSTEN-IRON-SULFUR CUBANE-LIKE CLUSTER [WFe_3S_4(S_2CNC_4H_8)s]·2DMF CONTAINING DITHIOCARBAMATO LIGANDS

<正> The title compound (Mr =1236.54) crystallizes in monoclinic space group C2/c with a =12.553(4),b=20.121(6),c=19.659(2)A,β=102.96(2)°,V=4839.1A3, Z = 4 and DC -1.697g/cm3. The structure was solved by direct methods.A full matrix least-squares refinement for 2197 reflections with I>3σ(I) gave final R and Rw of 0.064 and 0.076,respectively. The [WFe3S4] core of the cluster can be considered to be a [WFe3] tetrahedron capped by a sulfur atom on each face to fora a distorted cubane. The 57Fe Mossbauer spectrum indicates that there are two types of Fe atoms of ratio 2:1 in the cluster.     

Molybdenum-iron-sulfur clusters of nuclearities eight and sixteen, including a topological analogue of the P-cluster of nitrogenase

Transformations of the edge-bridged double cubane cluster [(Cl4cat)2(Et3P)2Mo2Fe6S8(PEt3)4] (1) under reducing conditions have been investigated as synthetic approaches to the clusters of nitrogenase. Cluster 1 is a versatile precursor to different Mo-Fe-S cluster types. The reaction system 1/K(C14H10) in THF yields the reduced cluster [(Cl4cat)2(Et3P)2Mo2Fe6S8(PEt3)4]1- (2), which as its crystalline Et4N+ salt retains the edge-bridged structure of 1. X-ray structural and M?ssbauer spectroscopic results indicate an unsymmetrical electron distribution with localized [MoFe3S4]2+,1+ cubane-type units. The system 1/2K(C14H10)/2HS- in THF/acetonitrile affords [(Cl4cat)4(Et3P)4Mo4Fe12S20K3(DMF)]5- (3), whose structure was determined as the Ph3PMe+ salt. The cluster consists of two isostructural Mo2Fe6S9 fragments connected by two mu 2-S bridges. Three potassium ions are bound between the two fragments. In each fragment, the iron atoms are present in tetrahedral FeS4 and the molybdenum atoms in octahedral MoO2PS3 coordination units, and two MoFe3(mu 3-S)3 cuboidal units are bridged by a common mu 6-S atom. The fragments have idealized mirror symmetry and are isostructural with two of the fragments present in the previously reported high-nuclearity cluster [(Cl4cat)6(Et3P)6Mo6Fe20S30]8- (4) (Osterloh, F.; Sanakis, Y.; Staples, R. J.; Münck, E.; Holm, R. H. Angew. Chem., Int. Ed. Engl. 1999, 38, 2066). On the basis of overall shape, atom connectivities, and metric features, the Mo2Fe6S9 fragment is a topological analogue of the P-cluster of nitrogenase in the PN (reduced) state. A third cluster type, formed as a minor byproduct in the reaction system leading to 2, was crystallographically identified as [(Cl4cat)2(Et3P)2Mo2Fe6S8(PEt3)4]4-, whose core is made up of two MoFe3(mu 3-S)3 cuboidal units bridged by two mu 2-S atoms and connected by a direct Fe-Fe bond. Full structural details and the redox properties of 2 and 3 are reported.     

The Synthesis and Crystallographic Characterization of Heterotrimetallic Linear Complex of [Et_4N][ (Ph_3P)_2{CuS_2WS_2Fe} Br_2]

1INTRoDUCTIONMolybdenum(Tungsten)-copper-sulfurandmolydenum(tungsten)-iron-sulfurcompoundshavebeenstudiedextensivelybecauseoftheirconnectionwithbiologicalprocesses[l,2j.Someheterotrimetalliccomplexeshavebeensynthesized,suchas[NEt'jtPh,p)sAgSzMoSzCu(CN))and[NEt'jtPh,P),AgS,MooCu(CN)jt3i,[l(CH,CH,)'j(PPh,)2{AgS2WS2Cu}(CN)jt4i,[(CH,CH2)4j(PPh,)2{AgS,WOCu}(CN)j('3,butheterotrimetal1iccomplexescontainingtungsten,copper,andironatomshaveseldombeenreported.Onecomplexofthiskindha…     

Tri- and pentanuclear tungsten-(mu-S)-M clusters (M = W, Cu, Ag)

The thiotungstate [Et4N]2[OW(WS4)2], [Et4N]2.1, containing the linear [[S2W(VI)(mu-S)2]2W(IV)=O] core, was prepared from [Et4N]2[WS4] in the presence of the sulfide scavenger Cd2+. Addition of 1,2-bis(o-diphenylphosphinophenyl)ethane (diphosphine) and Cu+ or Ag+ to solutions of 1 in MeCN/DMF led to coordination of the (diphosphine)Cu/Ag fragments to the terminal sulfido ligands of 1, yielding novel linear pentanuclear, heterometallic clusters [mu-[OW(IV)(DMF)(W(VI)S4)2][M(diphosphine)]2], 2 (M = Cu) and 3 (M = Ag). Along with 2, the trinuclear cluster [[mu-(W(VI)S4)[Cu(diphosphine)(2)]], 4, was also obtained. The molecular and crystal structures of [Et4N]2.1, 2.MeCN, 3.MeCN, and 4.2MeCN.CH2Cl2 have been determined.     

二核Fe/S化合物(Et4N)2[Fe2S2Br4]的合成与结构

标题化合物(Et4N)2[Fe2s2Br4](1)在VS/FeBr2/imnt2/Et4NCl反应体系中获得,它属于单斜晶系,空间群P21/n,主要晶胞参数为:α＝0.91193(2)nm,b=1.0837(3)nm,c=1.54360(1)nm,β=105.090(1),ν=1.4177(5)nm3,z=2,ρ=1.778g/cm3,μ＝6.841cm1,F(000)=748,结构精修结果为:R1=0.0287,wR=0.0640。簇阴离子[Fe2S2Br4]2含有一个菱形Fe2S2单元,铁的配位几何构型明显偏离了理想的Td对称性,导致整个阴离子的对称性降低为D2h.同时观察到它的Fe--Br键呈现反常加长倾向。     

Crystal Structure of Complex （Et4N）[VFe3S4Cl3（CH3CN）3]

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Reactions of synthetic [2Fe-2S] and [4Fe-4S] clusters with nitric oxide and nitrosothiols

The interaction of nitric oxide (NO) with iron-sulfur cluster proteins results in degradation and breakdown of the cluster to generate dinitrosyl iron complexes (DNICs). In some cases the formation of DNICs from such cluster systems can lead to activation of a regulatory pathway or the loss of enzyme activity. In order to understand the basic chemistry underlying these processes, we have investigated the reactions of NO with synthetic [2Fe-2S] and [4Fe-4S] clusters. Reaction of excess NO(g) with solutions of [Fe2S2(SR)4](2-) (R = Ph, p-tolyl (4-MeC6H4), or 1/2 (CH2)2-o-C6H4) cleanly affords the respective DNIC, [Fe(NO)2(SR)2](-), with concomitant reductive elimination of the bridging sulfide ligands as elemental sulfur. The structure of (Et4N)[Fe(NO)2(S-p-tolyl)2] was verified by X-ray crystallography. Reactions of the [4Fe-4S] clusters, [Fe4S4(SR)4](2-) (R = Ph, CH2Ph, (t)Bu, or 1/2 (CH2)-m-C6H4) proceed in the absence of added thiolate to yield Roussin's black salt, [Fe4S3(NO)7](-). In contrast, (Et4N)2[Fe4S4(SPh)4] reacts with NO(g) in the presence of 4 equiv of (Et4N)(SPh) to yield the expected DNIC. For all reactions, we could reproduce the chemistry effected by NO(g) with the use of trityl-S-nitrosothiol (Ph3CSNO) as the nitric oxide source. These results demonstrate possible pathways for the reaction of iron-sulfur clusters with nitric oxide in biological systems and highlight the importance of thiolate-to-iron ratios in stabilizing DNICs.     

Rearrangement of symmetrical dicubane clusters into topological analogues of the P cluster of nitrogenase: nature's choice?

Reaction schemes have been developed that lead to clusters having the topology of the PN cluster of nitrogenase. The single cubane clusters [(Tp)MFe3S4Cl3]z (M = Mo, z = 1-; M = V, z = 2-) react with PEt3 to give [(Tp)MFe3S4(PEt3)3]1+, which are reduced to the neutral edge-bridged double cubanes [(Tp)2M2Fe6S8(PEt3)4] with highly reduced (2[MFe3S4]1+) cores. Reaction of these clusters in acetonitrile with (Et4N)(HS) results in the formation of [(Tp)2Mo2Fe6S9(SH)2]3- and [(Tp)2V2Fe6S9(SH)2]4-. X-ray structures of the Et4N+ salts reveal the bridging pattern M2Fe6(mu2-S)2(mu3-S)6(mu6-S) in which two cuboidal MFe3(mu3-S)3 units share the common bridge atom mu6-S and are externally bridged by two mu2-S atoms. The M sites possess trigonal octahedral, and the Fe sites, distorted tetrahedral coordination. Hydrosulfide ligands and sulfide atoms simulate terminal cysteinate ligation and mu2 bridges, respectively, in the protein-bound cluster Fe8S7(mu2-SCys)2(SCys)4. The synthetic clusters have the same bridging pattern as the PN cluster and approach congruency with it. These clusters are the first molecular topological analogues of a PN cluster. Like the latter, they are substantially reduced (majority of Fe(II)).     

Hydroxide-promoted core conversions of molybdenum-iron-sulfur edge-bridged double cubanes: oxygen-ligated topological PN clusters

The occurrence of a heteroatom X (C, N, or O) in the MoFe7S9X core of the iron-molybdenum cofactor of nitrogenase has encouraged synthetic attempts to prepare high-nuclearity M-Fe-S-X clusters containing such atoms. We have previously shown that reaction of the edge-bridged double cubane [(Tp)2Mo2Fe6S8(PEt3)4] (1) with nucleophiles HQ- affords the clusters [(Tp)2Mo2Fe6S8Q(QH)2](3-) (Q = S, Se) in which HQ- is a terminal ligand and Q(2-) is a mu2-bridging atom in the core. Reactions with OH- used as such or oxygen nucleophiles generated in acetonitrile from (Bu3Sn)2O or Me3SnOH and fluoride were examined. Reaction of 1 with Et4NOH in acetonitrile/water generates [(Tp)2Mo2Fe6S9(OH)2]3- (3), isolated as [(Tp)2Mo2Fe6S9(OH)(OC(=NH)Me)(H2O)](3-) and shown to have the [Mo2Fe6(mu2-S)2(mu3-S)6(mu6-S)] core topology very similar to the P(N) cluster of nitrogenase. The reaction system 1/Et4NOH in acetonitrile/methanol yields the P(N)-type cluster [(Tp)2Mo2Fe6S9(OMe)2(H2O)](3-) (5). The system 1/Me3SnOH/F- affords the oxo-bridged double P(N)-type cluster {[(Tp)2Mo2Fe6S9(mu2-O)]2}5- (7), convertible to the oxidized cluster {[(Tp)2Mo2Fe6S9(mu2-O)]2}4- (6), which is prepared independently from [(Tp)2Mo2Fe6S9F2(H2O)](3-)/(Bu3Sn)2O. In the preparations of 3-5 and 7, hydroxide liberates sulfide from 1 leading to the formation of P(N)-type clusters. Unlike reactions with HQ-, no oxygen atoms are integrated into the core structures of the products. However, the half-dimer composition [Mo2Fe6S9O] relates to the MoFe7S9 constitution of the putative native cluster with X = O. (Tp = hydrotris(pyrazolyl) borate(1-)).