含钼(钨)锡键的四元金属有机杂环化合物的合成与反应研究

通过三苯基锡基-双(3,5-二甲基吡唑)甲烷与羰基钼的反应合成了钼锡键合的四元金属杂环化合物CH(3,5- Me₂Pz)₂Mo(CO)₃SnPh₃ (Pz＝1-吡唑基). 当用叔丁基异腈处理该化合物及其钨类似物时, 伴随着有机锡结构单元的丢失, 金属钼(钨)上发生还原消除并分解得到化合物CH₂(3,5-Me₂Pz)₂M(CO)₃(CNBu-t) (M为Mo或W). 另外, 该化合物与三苯基膦或亚磷酸甲酯及异丙酯反应时, 只发生羰基取代反应得到化合物CH(3,5-Me₂Pz)₂Mo(CO)₂(PR₃)SnPh₃ (R为苯基、甲氧基及异丙氧基). 而用亚磷酸苯酯与之反应, 除得到羰基取代产物外, 还伴随着P-O/C键的交换, 得到金属钼上还原消除的产物(PhO)₂PCH(3,5-Me₂Pz)₂Mo(CO)₃.     

乙烯基锡修饰的双吡唑甲烷第六族金属羰基化合物的合成与反应

通过双吡唑基甲基锂与二苯基乙烯基碘化锡的反应, 合成了桥头碳上带有乙烯基锡修饰的双吡唑甲烷配体。在回流的THF中这些乙烯基锡修饰的双吡唑甲烷配体(R3SnCHPz2, R3Sn为三乙烯基锡或二苯基乙烯基锡;Pz代表取代吡唑)与M(CO)5THF (M = Mo或W)反应产生杂双金属化合物R3SnCHPz2M(CO)3。在这些化合物中,一个乙烯基以h2方式配位到金属钼或钨上,双吡唑甲烷表现为一个三齿k3-(p,N,N)配体。(CH2=CH)3SnCH(3,5-Me2Pz)2W(CO)3和Ph2(CH2=CH)SnCH(3,5-Me2Pz)2W(CO)3与I2的反应也被研究。前者给出化合物CH2(3,5-Me2Pz)2W(CO)4,而后者随着有机锡的丢失产生四元金属杂环化合物CH(3,5-Me2Pz)2W(CO)3I。用PhSNa处理该四元金属杂环化合物导致碘负离子被取代,得到化合物CH(3,5-Me2Pz)2W(CO)3SPh。     

不对称取代双(吡唑)甲烷VIB羰基金属化合物的合成及表征

3-苯基吡唑与二溴甲烷在相转移催化下反应,得到(3-苯基吡唑-5'-苯基吡唑)甲烷(1)和双(3-苯基吡唑)甲烷(2)的混合物.当该混合配体与M(CO)₆(M=Cr,Mo,W)在光照下反应时,分离得到了不对称取代的(3-苯基吡唑-5'-苯基吡唑)甲烷四羰基铬(3),钼⑷和钨(5).用X-射线衍射测定了化合物5的晶体结构.结果表明,该晶体属于单斜晶系,P2(1)/n空间群,a=1.7976(7) rnn,b=1.3210(5) nm, c=1.8681(7) nm;β=98.293(8)°, V=4.390(3) nm³, Z=8,最终结构偏离因子[I>2σ(I)]=0.0516, Rw=0.0898, GOF=0.879.两个苯基分别处于两个吡唑的3位及5'位.     

三(2-甲基-2-苯基丙基)锡衍生物的合成及生物活性研究

三(2-甲基-2-苯基丙基)锡氧化物(Torque,苯丁锡,[(C₆H₅CMe₂CH₂)₃Sn]₂O)是-个已商品化的有机锡杀螨剂^[1]。为了研究三烃基锡衍生物中阴离子配体对生物活性的影响,本文用苯丁锡与酚或羧酸反应,合成了四个系列的含氧三(2-甲基-2-苯基丙基)锡衍生物。     

基于偶氮桥连的新型双铁羰基配合物:Fe2(N2C5H10)(CO)6-x (PR3)x的合成及衍生

具有五元环结构的偶氮化合物4,4-二甲基-4,5-二氢-3H-吡咯（N₂C₅H₁₀）,与Fe₃（CO）₁₂在甲苯中加热回流反应,生成双铁六羰基配合物Fe₂（N₂C₅H₁₀）（CO）₆（1）.反应中N=N双键被还原,配体以（N₂C₅H₁₀）^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Me₃NO存在条件下,1和单齿膦配体PR₃反应生成Fe₂（N₂C₅H₁₀）-（CO）₅（PR₃）（PR₃=PPh₃,2a;PCy₃,2b）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-C₂H₄（PPh₂）₂]和dppbz[dppbz=1,2-C₆H₄（PPh₂）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Fe₂（N₂C₅H₁₀）（CO）₄（μ-dppe）（3a）;而与刚性较大的dppbz反应时,Fe₂（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Fe₂（N₂C₅H₁₀）（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Fe₂（SR）₂（μ-CO）-（CO）_5-xL_x的重要挑战.该类Fe₂（NR）₂（CO）_6-x（PR₃）_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.     

桥头碳上氮杂芳基功能化的双吡唑甲烷与羰基钨反应

研究了(氮甲基咪唑-2-基)双(3,5-二甲基吡唑)甲烷(L1),2-吡啶基双(3,5-二甲基吡唑)甲烷(L2)及4-吡啶基双(3,5-二甲基吡唑)甲烷(L3)与羰基钨的反应,合成了一系列以单齿,双齿及三齿氮配位的羰基金属衍生物LW(CO)5(L=L1或L3),LW(CO)4(L=L1,L2或L3)和LW(CO)3(L=L1或L2)。核磁,红外及X-射线单晶衍射分析表明这3种配体表现出了可变的配位方式。在LW(CO)5中,当配体为L1时,其倾向于通过咪唑氮与金属配位,而为L3则倾向于利用吡啶氮与金属作用;在LW(CO)4中,配体L1表现为通过咪唑氮和吡唑氮原子配位的[N,N′]双齿配体,而L2和L3表现为通过吡唑氮原子配位的[N,N]双齿配体;在LW(CO)3中,L1和L2起着[N,N,N′]三齿螯合配体的作用。     

桥头碳上氮杂芳基功能化的双吡唑甲烷与羰基钨反应（英文）

研究了(氮甲基咪唑-2-基)双(3,5-二甲基吡唑)甲烷(L1),2-吡啶基双(3,5-二甲基吡唑)甲烷(L2)及4-吡啶基双(3,5-二甲基吡唑)甲烷(L3)与羰基钨的反应,合成了一系列以单齿,双齿及三齿氮配位的羰基金属衍生物LW(CO)5(L=L1或L3),LW(CO)4(L=L1,L2或L3)和LW(CO)3(L=L1或L2)。核磁,红外及X-射线单晶衍射分析表明这3种配体表现出了可变的配位方式。在LW(CO)5中,当配体为L1时,其倾向于通过咪唑氮与金属配位,而为L3则倾向于利用吡啶氮与金属作用;在LW(CO)4中,配体L1表现为通过咪唑氮和吡唑氮原子配位的[N,N′]双齿配体,而L2和L3表现为通过吡唑氮原子配位的[N,N]双齿配体;在LW(CO)3中,L1和L2起着[N,N,N′]三齿螯合配体的作用。     

双(3,5-二甲基-4-苄基吡唑)甲烷ⅥB族羰基化合物的合成及反应

通过 3 ,5 -二甲基 -4-苄基吡唑与二溴甲烷在相转移催化下反应 ,合成了一个新的多吡唑烷配体双 (3 ,5 -二甲基 -4-苄基吡唑 )甲烷 .该配体与 M(CO) 6 (M=Cr,Mo,W)在光照下反应可以得到双 (3 ,5 -二甲基 -4-苄基吡唑 )甲烷四羰基铬 (2 )、钼 (3 )和钨 (4 ) .用 Sn Cl4 处理化合物 3和 4可以高产率地制得含 Mo(W)— Sn键的杂双金属配合物 .用 X射线衍射法测定了化合物 4与 Sn Cl4 反应产物 6的晶体结构 .结果表明 ,该晶体属三斜晶系 ,P1空间群 ,晶胞参数 a=1 .0 92 9(9) nm,b=1 .2 82 (1 ) nm,c=1 .2 82 (1 ) nm,α=1 0 2 .3 5 (1 )°,β=1 0 8.62 (1 )°,γ=97.0 0 (1 )°,V=1 .799(3 ) nm3,Z=2 ,最终结构偏离因子 R=0 .0 5 8,w R=0 .1 0 1 5 ,GOF=0 .90 5 .六元金属杂环 W— N— N— C— N— N为船式构象 ,分子中没有氯桥存在 .     

(p-CH3OC6H4)2TeO存在下M2(CO)10(M=Mn,Re)的CO取代反应动力学研究

测定了(p-CH₃OC₆H₄)₂TeO存在下M₂(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M₂(CO)₁₀和(p-CH₃OC₆H₄)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(CH₃)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(CH₃)₃NO和(p-CH₃OC₆H₄)₂TeO存在下影响M₂(CO)₁₀的CO取代反应速率的因素。     

基于1-(2-吡啶甲基)-1,2,4-三唑的金属有机化合物的合成及反应研究(英文)

合成了1-(2-吡啶甲基)-1,2,4-三唑(L)并研究了其与有机锡和羰基钼(钨)的配位反应,合成了通过三唑4位氮原子以单齿形式配位的有机锡衍生物L2SnR2Cl2(R=Me,n-Bu或Ph)和羰基金属配合物LM(CO)5(M=Mo或W),以及N,N螯合双齿配位的四羰基金属配合物LM(CO)4。当用氯化苄处理L时,制得了相应的三唑盐,该盐用氧化银处理后与M(CO)5THF或M(CO)4(NHC5H10)2(NHC5H10为哌啶)反应,得到了基于三唑的氮杂环卡宾衍生物L′M(CO)5和L′M(CO)4(L′=1-(2-吡啶甲基)-4-苄基-1,2,4-三唑-5-碳烯)。X-射线单晶衍射分析表明,在L′M(CO)5中氮杂环卡宾配体L′表现为通过卡宾碳配位的单齿配体;而在L′M(CO)4中,L′表现为通过卡宾碳和吡啶氮原子配位的螯合[C,N]双齿配体。     

The modification of bis(pyrazol-1-yl)methanes by chalcogen (S and Se) and their related reactions with organotin chloride and M(CO)5THF (M = Mo and W)

The modification of bis(pyrazol-1-yl)methane by sulfur or selenium on the methine carbon has been successfully carried out by the reaction of the bis(pyrazol-1-yl)methide anion, prepared in situ by the reaction of bis(pyrazol-1-yl)methane with n-BuLi, with elemental sulfur or selenium. These bis(pyrazol-1-yl)methylthiolate or selenolate anions reacted with Ph₂SnCl₂ to form new organotin derivatives CH(3,5-Me₂Pz)₂ESnPh₂Cl (Pz = pyrazol-1-yl, E = S (1) or Se (2)), which have been characterized by NMR, IR and elemental analysis. The molecular structure of 2 determined by X-ray structure analysis indicates that bis(3,5-dimethylpyrazol-1-yl)methylselenolate is a bidentate monoanionic κ²-[N,Se] chelating ligand. The treatment of CH(3,5-Me₂Pz)₂ESnPh₂Cl with W(CO)₅THF resulted in the decomposition of ligands to yield pyrazole derivative of (3,5-Me₂PzH)W(CO)₅, while direct treatment of bis(pyrazol-1-yl)methylthiolate or selenolate anions with M(CO)₅THF (M = Mo or W) formed their tricarbonyl metal anions . Succedent reaction of these carbonyl metal anions with Ph₂SnCl₂ or Ph₃SnCl yielded heterobimetalic compounds CH(Pz)₂EM(CO)₃SnPh_nCl_3−n (n = 2 or 3), which have also been characterized by ¹H NMR, IR and elemental analysis. The structure of CH(3,4,5-Me₃Pz)₂SW(CO)₃SnPh₃ (8) has been confirmed by X-ray single crystal diffraction, showing that bis(3,4,5-trimethylpyrazol-1-yl)methylthiolate acts as a tridentate, monoanionic κ³-[N,S,N] chelating ligand.     

Functionalized bis(pyrazol-1-yl)methanes by organotin halide on the methine carbon atom and their related reactions

The modification of bis(pyrazol-1-yl)methanes by organotin halide on the methine carbon atom has been successfully carried out, and their related reactions have also been studied. Bis(3,5-dimethylpyrazol-1-yl)(iododiphenylstannyl)methane [Ph₂ISnCH(3,5-Me₂Pz)₂] can be obtained by the selective cleavage of the Sn-C_sp² bond in bis(3,5-dimethylpyrazol-1-yl)triphenylstannylmethane with I₂ in a 1:1 molar ratio, while {di(tert-butyl)chlorostannyl}bis(3,5-dimethylpyrazol-1-yl)methane [(t-Bu)₂ClSnCH(3,5-Me₂Pz)₂] and {di(tert-butyl)chlorostannyl}bis(3,4,5-trimethylpyrazol-1-yl)methane [(t-Bu)₂ClSnCH(3,4,5-Me₃Pz)₂] are easily prepared by the reaction of the bis(3,5-dimethylpyrazol-1-yl)methide or bis(3,4,5-trimethylpyrazol-1-yl)methide anion with di(tert-butyl)tin dichloride. The molecular structure of [(t-Bu)₂ClSnCH(3,5-Me₂Pz)₂] determined by X-ray structure analysis indicates that bis(3,5-dimethylpyrazol-1-yl)methide acts as a bidentate monoanionic κ²-[C,N] chelating ligand. Reaction of these bis(pyrazol-1-yl)methanes functionalized by organotin halide with W(CO)₅THF results in the oxidative addition of the relative electrophilic Sn-X (X = Cl or I) bond instead of the Sn-C_sp³ bond to the tungsten(0) atom, yielding new metal-metal bonded complexes R₂SnCHPz₂W(CO)₃X (R = Ph or t-Bu, Pz represents substituted pyrazol-1-yl). Furthermore, treatment of the oxidative addition product (t-Bu)₂SnCH(3,5-Me₂Pz)₂W(CO)₃Cl with n-BuLi results in known complex CH₂(3,5-Me₂Pz)₂W(CO)₄ with the loss of the organotin fragment. In addition, reaction of Ph₂ISnCH(3,5-Me₂Pz)₂ with 2-PySNa (Py = pyridyl) leads to the replacement of iodide by 2-PyS⁻ anion to give Ph₂(2-PyS)SnCH(3,5-Me₂Pz)₂, which subsequently reacts with W(CO)₅THF to result in the decomposition of this ligand, also yielding the known bis(3,5-dimethylpyrazol-1-yl)methane derivative of CH₂(3,5-Me₂Pz)₂W(CO)₄.     

Reactivity of bis(pyrazol-1-yl)methanes functionalized by 2-hydroxyphenyl and 2-methoxyphenyl on the methine carbon atom with W(CO)5THF

Reactions of 2-hydroxyphenyl and 2-methoxyphenylbis(pyrazol-1-yl)methanes as well as 2-hydroxyphenyl and 2-methoxyphenylbis(3,5-dimethylpyrazol-1-yl)methanes with W(CO)₅THF have been carried out. Heating 2-hydroxyphenylbis(pyrazol-1-yl)methane (L¹) with W(CO)₅THF in THF at reflux yielded complex (L¹)W(CO)₄.L¹, while similar reaction of 2-hydroxyphenylbis(3,5-dimethylpyrazol-1-yl)methane (L²) with W(CO)₅THF resulted in the cleavage of a C_sp3-N bond to generate 1,2-bis(2-hydroxyphenyl)-1,2-bis(3,5-dimethylpyrazol-1-yl)ethane (L) and pyrazole derivative W(CO)₅(3,5-Me₂PzH) (Pz = pyrazol-1-yl). These two fragments were connected together through strong O…H-N and O-H…N hydrogen bonds to form complex L.[W(CO)₅(3,5-Me₂PzH)]₂. The analogous results were observed in the treatment of 2-methoxyphenylbis(pyrazol-1-yl)methane (L³) with W(CO)₅THF, which gave product L′.[W(CO)₅(PzH)]₂ (L′ = 1,2-bis(2-methoxyphenyl)-1,2-bis(pyrazol-1-yl)ethane) as well as certain amount of complex (L³)W(CO)₄. In addition, during the reaction of 2-methoxyphenylbis(3,5-dimethylpyrazol-1-yl)methane (L⁴) with W(CO)₅THF, partial decomposition reactions took place to yield complexes (L⁴)W(CO)₄ and W(CO)₅(3,5-Me₂PzH), but no hydrogen bond was found between these two moieties.     

Synthesis, structure and characterization of M---Sn (M=Mo, W) bonded heterobimetallic complexes containing bis(pyrazol-1-yl)methane ligands

The reaction of bis(pyrazol-1-yl)methane tetracarbonylmolybdenum(0) or tungsten(0) complexes with RSnCl₃ (R=Ph, Cl) at room temperature yielded heterobimetallic complexes CH₂(Pz)₂M(CO)₃(Cl)(SnCl₂R) (Pz represents substituted pyrazole; M=Mo or W; R=Ph or Cl) in good yields, which have been characterized by elemental analysis, ¹H NMR and IR spectroscopy. The reaction of bis(3,5-dimethyl-4-halopyrazol-1-yl)methane tetracarbonyl tungsten with PhSnCl₃ did not take place even in refluxing CH₂Cl₂. The electronic and steric characteristics of substituents on the pyrazole ring remarkably influence the structures of the products. The structures of CH₂(3,5-Me₂-4-BrPz)₂W(CO)₃(Cl)(SnCl₃) (8) and CH₂(4-BrPz)₂Mo(CO)₃(μ-Cl)(SnCl₂Ph) (17) (Pz: pyrazole) determined by X-ray crystallography show that no chlorine-bridged W---Sn bond is observed in complex 8, while one chlorine-bridged Mo---Sn bond exists in complex 17. The Sn---M bond length is 2.7438(5) Å in complex 8 (W---Sn) and 2.7559(4) Å in complex 17 (Mo---Sn).     

Synthesis and crystal structures of Group 6 metal carbonyl complexes containing S-rich bis(pyrazol-1-yl)methane ligands

The reaction of 3(5)-methylthio-5(3)-phenylpyrazole with dibromomethane under phase-transfer catalytic conditions only affords a new ligand, bis(3-phenyl-5-methylthiopyrazol-1-yl)methane. However, the reaction of 3(5)-methylthio-5(3)-p-methoxyphenylpyrazole or 3(5)-methylthio-5(3)-tert-butylpyrazole with dibromomethane under the same conditions yields three isomers, respectively, indicating that the substituents significantly affect the steric and electronic properties of pyrazole ring during the formation of ligands. Treatment of these potential polydentate ligands with M(CO)₆ (M=Cr, Mo or W) under UV irradiation at room temperature affords (NN)M(CO)₄ derivatives, in which some complexes contain asymmetric substituted bis(pyrazol-1-yl)methane ligands. The X-ray crystal structure analyses indicate that the sulfur atoms in these complexes do not take part in the coordination to the metal centers, and S-rich bis(pyrazol-1-yl)methanes actually act as bidentate chelating ligands by two nitrogen atoms. It is also interesting that in order to reduce the repulsion of methyl groups with carbonyls, the methyl groups in these complexes are oriented away from the metal centers.     

New multidentate heteroscorpionate ligands: N-Phenyl-2,2-bis(pyrazol-1-yl)thioacetamide and ethyl 2,2-bis(pyrazol-1-yl)dithioacetate as well as their derivatives

New multidentate heteroscorpionate ligands, N-phenyl-2,2-bis(3,5-dimethylpyrazol-1-yl)thioacetamide PhHNCSCH(3,5-Me₂Pz)₂ (1), N-phenyl-2,2-bis(3,4,5-trimethylpyrazol-1-yl)thioacetamide PhHNCSCH(3,4,5-Me₃Pz)₂ (2), and ethyl 2,2-bis(3,5-dimethylpyrazol-1-yl)dithioacetate EtSCSCH(3,5-Me₂Pz)₂ (8), have been synthesized and their coordination chemistry studied. These heteroscorpionate ligands can act as monodentate, bidentate, or tridentate ligands, depending on the coordinate properties of different metals. Reaction of W(CO)₆ with 1 or 2 under UV irradiation yields monosubstituted carbonyl tungsten complexes W(CO)₅L (L = 1 or 2), in which N-phenyl-2,2-bis(pyrazol-1-yl)thioacetamide acts as a monodentate ligand by the s-coordination to the tungsten atom. In addition, these monosubstituted tungsten complexes have also been obtained by heating ligand 1 or 2 with W(CO)₅THF in THF. While similar reaction of Fe(CO)₅ with 1, 2, or 8 under UV irradiation results in tricarbonyl iron complexes PhHNCSCH(3,5-Me₂Pz)₂Fe(CO)₃ (5), PhHNCSCH(3,4,5-Me₃Pz)₂Fe(CO)₃ (6), and EtSCSCH(3,5-Me₂Pz)₂Fe(CO)₃ (9), respectively, in which N-phenyl-2,2-bis(pyrazol-1-yl)thioacetamide or ethyl 2,2-bis(pyrazol-1-yl)dithioacetate acts as a bidentate ligand through one pyrazolyl nitrogen atom and the CS π-bond in an η²-C,S fashion side-on bonded to the iron atom to adopt a neutral bidentate κ²-(π,N) coordination mode. Treatment of the lithium salt of 1 with Co(ClO₄)₂ · 6H₂O gives complex [PhNCSCH(3,5-Me₂Pz)₂]₂Co(ClO₄) with the oxidation of cobalt(II) to cobalt(III), in which N-phenyl-2,2-bis(3,5-dimethylpyrazol-1-yl)thioacetamide acts as a tridentate monoanionic κ³-(N,N,S) chelating ligand by two pyrazolyl nitrogen atoms and the sulfur atom of the enolized thiolate anion.     

Crystal Structure of CH(3,5-Me2-4-EtPz)2W(CO)3SnPh3·0.25C6H6 (Pz = Pyrazol-1-yl)

The reaction of triphenylstannyl-bis(3,5-dimethyl-4-ethylpyrazol-1-yl)methane with W(CO)5THF yields the title compound (C37.5H39.5N4O3SnW, Mr = 896.79) which is of triclinic,space group P1 with a = 9.755(3), b = 13.696(4), c = 14.359(5) A, α = 96.202(7), β= 93.313(6), γ=94.845(6)°, V = 1896(1) A3, Z = 2, Dc = 1.571 g/cm3, λ(MoKα) = 0.71073 A, μ= 3.728 mm-1,F(000) = 881, R = 0.0491 and wR = 0.0856 for 4242 observed reflections (I≥2σ(I)). The crystalstructural analysis indicates that bis(3,5-dimethyl-4-ethylpyrazol-1-yl)methide acts as a tridentate monoanionic K3-[N,C,N] chelating ligand, and four-membered metallacycles are found in this heterodinuclear complex.     

Crystal Structure of CH(3,5-Me_2-4-EtPz)_2 W(CO)_3SnPh_3·0.25C_6H_6 (Pz = Pyrazol-1-yl)

1 INTRODUCTION As a kind of popular polydentate nitrogen donor ligands, poly(pyrazol-1-yl)alkanes, especially bis(pyrazol-1-yl)methanes, have been widely used for many years to synthesize main group[1, 2] and transition metal complexes[3, 4]. Recent inve…