双烯酮亚胺基钇二氯化物LYCl2(THF)2的合成、表征及晶体结构[L=2,4-二苯胺基-2-戊烯基]

无水YCl3与一倍量的LLi(L=2,4 二苯胺基 2 戊烯基)在甲苯 四氢呋喃(THF)中反应,分离得到了双烯酮亚胺稀土二氯化物LYCl2(THF)2,并测定了其晶体结构。配合物属正交晶系,Pna21空间群,晶胞参数为a=1.9612(5)nm,b=0.9582(3)nm,c=1.4203(4)nm,V=2.669(1)nm3,Z=6,Dc=1.377mg·m-3,μ=2.408mm-1(MoKα),F(000)=1144,R=0.0358,wR=0.0640。中心金属钇原子与双烯酮亚胺基上的2个氮原子、2个氯原子以及2个四氢呋喃上的氧原子配位,形成一个六配位的、稍扭曲的八面体几何构型的配合物。     

中性均配型稀土胺化物Yb(NPh_2)_3(THF)_2的合成、表征及晶体结构

无水YbCl3与三倍量的LiNPh2 在四氢呋喃 (THF)中反应 ,合成了中性均配型稀土胺化物Yb(NPh2 ) 3(THF) 2 。产物经元素分析、红外光谱表征 ,并测定了其晶体结构。配合物属单斜晶系 ,P2 1 /n空间群 ,晶胞参数为a =1 2 0 5 2 ( 2 )nm ,b =1 9369( 3)nm ,c =1 65 2 3( 2 )nm ,β =92 79( 1)°,V =3 85 2 4( 9)nm3,Z =4,Dc=1 417g·cm- 3,μ =2 4 67cm- 1 (MoKα) ,F( 0 0 0 ) =1668,R =0 0 36,Rw=0 0 39。3个二苯胺基的氮原子和两个THF的氧原子与金属镱配位 ,形成五配位的扭曲的三角双锥几何构型。平均的Yb—N键长为 0 2 2 19( 6)nm。     

环戊烷基茚基氯化钇(1-C5H9C9H6)2-Y(μ-Cl)2Li(THF)2的合成及其晶体结构

无水YCl3与1-环戊烷基茚基锂以1/2的摩尔比在THF中反应合成了二(1-环戊烷基茚基)氯化钇(C5H9C9H6)2Y(μ-Cl)2Li(THF)2,产物用元素分析、红外光谱及XRD进行表征. 结果表明,其晶体属于正交晶系,Pna2(1)空间群,a =1.648 2(7) nm,b =1.877 2(8) nm,c =1.131 7(5) nm,V =3.501(3) nm3,Z=4,Dc=1.285 Mg/m3,最终的偏离因子R=0.068 3,Rw=0.114 3.     

中性均配型稀土胺化物Yb（NPh2）3）THF）2的合成、表征及晶体结构

无水YbCl3与三倍量的LiNPh2的在四氢呋喃（THF）中反应,合成了中性均配型稀土胺化物Yb(NPh2)3(THF)2。产物经元素分析,红外光谱表征,并测定了其晶体结构。配合物属单斜晶系,P21／n空间群,晶胞参数为a=1.2052(2)nm,b=1.9369(3)nm,c=1.6523(2)nm,β＝92.79(1),V=3.8524(9)nm^3,Z=4,Dc=1.417g.cm^-3,μ=24.67cm^-1(MoKa),F(000)=1668,R=0.036,Rw=0.039,3个二苯胺基的氮原子和两个THF的氧原子与金属镱配位,形成五配位的扭曲的三角双锥几何构型,平均的Yb-N键长为0．2219(6)nm。     

[Flu(Me)2CCp]2Yb(μ-Br)2Li(THF)2·THF的合成和晶体结构

为考察取代环戊二烯基或桥联环戊二烯基有机稀土化合物的性质,研究了碳桥联芴基环戊二烯基配体与卤化稀土的反应,其中,[2-(9-芴基)异丙基]环戊二烯基锂[Flu(Me)2CCpLi]与三溴化镱(YbBr3)在四氢呋喃(THF)中反应,分离得到了标题配合物[Flu(Me)2CCp]2Yb(μ-Br)2Li(THF)2·THF.X射线单晶结构测定表明配合物属单斜晶系,空间群为P2(1)/n,晶胞参数为a=1.4676(3) nm,b=1.2618(4) nm,c=2.9736(9) nm,β=98.172(18)°,Z=4,V=5.451(2) nm3,Mr=1098.84,Dc=1.339 mg·m-3,R=0.0695,wR=0.1721.中心Yb原子分别与两个环戊二烯基和两个溴原子成键,形成扭曲的四面体配位构型.Yb-Br1和Yb-Br2键长分别为0.2765(1)和 0.2738(1) nm,两个环戊二烯基平面的夹角为125.7°,中心Yb原子与两个环戊二烯基环中心的平均距离分别为0.232和0.231 nm.     

茂基稀土胺化物与异氰酸正己酯的反应-{(MeC5H4)2Yb[OC(NPh2)N(n-hexyl)]}2的合成及表征

茂基稀土胺化物(MeCp)2YbNPh2(THF)与异氰酸正己酯(n-HexylNCO)按11摩尔比反应, 分离出产物{(MeC5H4)2Yb[OC(NPh2)N(n-hexyl)]}2. 产物经元素分析和核磁共振表征, 并测定了其晶体结构. 配合物属三斜晶系, R-3空间群, 晶胞参数为a=2.9533(11) nm, b=2.9533(11) nm, c=1.5873(6) nm, V=11.9896(80) nm3, Z=9, Dc=1.562 mg·m-3, μ=3.536 mm-1 (Mo Kα), F(000)=5670, R=0.034, Rw=0.064. 该化合物具有二个对称氧桥的双分子结构, 并存在着由氮原子向中心金属镱分子内配位而形成的三环骨架, 中心金属镱的配位数是九, 整个分子呈中心对称.     

利用氧化加成反应合成[Cu(C_6H_5COO)_2(C_5H_5N)_2(H_2O)]

室温下 ,金属铜粉和过氧化苯甲酰进行氧化加成反应合成了铜化合物 [Cu(C6H5COO) 2 (C5H5N) 2 (H2 O) ](1 )。通过元素分析、电导、红外光谱等方法对配合物进行了表征 ,并经X 射线单晶结构分析确定了配合物的结构 ,晶体属单斜晶系 ,空间群Cc ,a =0 .60 78(4) ,b =1 .5879(4) ,c =2 .30 91 (3)nm ,β =97.61 (2 )°,Z =4,V =2 .2 0 91nm3,R =0 .0 30 7,中心铜原子由单齿配位的苯甲酸根的氧原子和吡啶的氮原子及来自水分子的氧原子形成四方锥配位结构。     

(ArO)2Sm(THF)4催化N-苯基马来酰亚胺聚合

发现二价稀土配合物二 ( 2 ,6 二叔丁基 4 甲基苯氧基 )钐 [(ArO) 2 Sm (THF) 4]能较好地引发N 苯基马来酰亚胺 (N PMI)的聚合 ,溶剂对聚合的影响较大 ,在四氢呋喃中聚合转化率最高 ,且聚合转化率随单体浓度的提高而提高 ,而温度对聚合的影响不大。     

(C5H5)2NdCl·2LiCl 与正丁基锂的反应: [Li(DME)3][(C5H5)3Nd(μ-H)Nd(C5H5)3]的合成及其晶体结构

研究了(C5H5)2NdCl·2LiCl与正丁基锂在THF溶液中的反应, 并从该反应液中分离到了钕的氢化物[Li(DME)3][(C5H5)3Nd(μ-H)Nd(C5H5)3] 1. 化合物1经X射线单晶结构测定表明属单斜晶系, 空间群P21/c, 晶胞参数为a=0.9670(2) nm, b=2.1001(5) nm, c=2.1279(7) nm, β=90.89(2)°, Z=4, V=4.321 (2) nm3, Mr=957.36, Dc=1.47 g·cm-3, F(000)=1936, R=0.094, wR=0.100. 1的晶胞中包含两个独立的晶体分子, 每一分子由阴阳离子对[Li(DME)3]+和[(C5H5)3Nd(μ-H)Nd(C5H5)3]-组成. 钕原子与3个η5-C5H5基团配位, 且两个(C5H5)3Nd经氢桥键相连构成阴离子. Nd1-H和Nd2-H键长均为0.218(1) nm.     

配合物[Cu_2(TS)(H_2O)]·H_2O的自组装制备、晶体结构和电化学性质

利用单核配合物Na2 CuTS·H2 O在溶剂中的不稳定性质 ,自分解并重新组装得到了双核配合物 [Cu2 (TS)(H2 O) ]·H2 O .配合物为单斜晶系 ,空间群P2 1/C ,晶胞参数为a =0 .80 830 (16 )nm ,b =1.70 79(3)nm ,c =1.4 0 73(3)nm ,β =10 5 .0 8(3)° ,V =1.86 5 4 (6 )nm3 ,Z =4 ,最终一致性因子R =0 .0 6 4 4 .该分子结构为双核单元 ,金属原子通过两个酚氧原子桥联在一起 .结合晶体结构对配合物作了电化学研究     

二(2,6-二叔丁基-4-个甲基苯氧基)钐催化丙交酯开环聚合

聚丙交酯（PLA）可以生物降解，产物无毒，可用于外科手术的缝合线、人造器官以及药物缓释等方面，因此引起了人们的广泛注意．丙交酯的开环聚合是合成聚丙交酯的一种方便方法，所用的催化剂主要是主族及副族金属的配合物，如双金属氧桥配合物［‘j，烷基金属有机化合物［‘j，异丙氧基铝［’‘以及叶琳铝「“等．最近，关于三价烷氧基稀土化合物作为单组份催化剂催化丙交酯开环聚会已有报道［’·’‘．我们发现两价芳氧基稀土化合物（ArO）。Sin（THF）。（ArO一2，已二叔丁基一个甲基苯氧基）也可以有效地催化丙文酯的开环聚合．本…     

Synthesis and Crystal Structure of [（ArO）2Sm（OPPh3）（μ—OH）]2（ArO=2,6—tBu—4—Me—C6H2O）

1 INTRODUCTION In recent years, the syntheses, structures and reactivities of aryloxo lanthanide complexes have attracted a great deal of attention due to their various applications as homogeneous catalysts for organic reactions and precursors for organolan- thanide syntheses[1]. However, the reactivity of divalent lanthanide aryloxides has seldom been studied[2]. We have previously reported that (ArO)2- Sm(THF)4 (ArO = OC6H2-2,6-di-tert-butyl-4-Me) can efficiently initiate the poly…     

Synthesis and Crystal Structure of [(ArO)_2(THF)Sm(μ-OH)]_2·2THF(Ar=C_6H_(2-)~tBu_3-2,4,6)

1 INTRODUCTION Sm(II) chemistry has been extensively studied due to the strong reduction potential of this 4f6 ion[1]. The transformation of unsaturated substrates by Sm (II) complexes into products with unusual structures is one of the most interesting research areas. For the successful examples reported, Sm(II) starting mate- rials were restricted primarily to cyclopentadienyl complexes[2]. The reactivity of Sm(II) complex with phenolate ligands has seldom been explored. Recen- tl…     

配合物(ArO)2Yb(NPh2)2K(THF)4(Ar=C6H2-t-Bu3-2,4,6)的合成、分子结构和催化行为

Reaction of anhydrous YbC13 with 2 equiv, of sodium 2,4,6-tri-tert-butylphenoxide (ArONa, Ar=C6H2-t-Bu3-2,4,6) and 2 equiv, of potassium diphenyl amide in THF afforded the first bis(aryloxo) amido-lanthanide complex of (ArO)2Yb(NPh2)2K(THF)4 (1). In 1, the ytterbium and potassium were bridged via diphenyl amido ligands.The ytterbium metal center was coordinated to two oxygen atoms of aryloxide ligands and two nitrogen atoms of diphenyl amido ligands in a conventional distorted tetrahedral fashion, while the potassium interacted in η^2-fashion with two phenyl rings of the diphenyl amido ligands besides four THF molecules. 1 displayed moderate catalytic activities for the polymerization of methyl methacrylate and acrylonitrile.     

The rearrangement of phosphitohydrazide ligand [(ArO)2P-NPh-NPh-] into iminophosphoranate anion [(PhNP(OAr)2-NPh-] {(ArO)2P = [CH2(BuMeC6H2O)2P]} in coordination sphere of divalent cobalt

The reaction of bromophosphite (ArO)₂PBr {(ArO)₂P = CH₂(6-^tBu-4-Me-C₆H₂O)₂P} with lithium salt of 1,2-diphenylhydrazine gave phosphitohydrazine (ArO)₂P-NPh-NPhH (2) in 64% yield. The last one reacted with Co[N(SiMe₃)₂]₂ to afford cobalt(II) iminophosphoranate (PhNP(OAr)₂-NPh-)₂Co (3), which is the result of isomerisation of the phosphitohydrazide ligand in coordination sphere of divalent cobalt.     

ChemInform Abstract: The Thermodynamic Stability of ArO4

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Low coordinate germanium and tin compounds (ArO)2ME and (ArO)2MM′Ln M=Ge, Sn; E=S, Se, –NSiMe3 M′=Cr, W, Fe, Pt [Ar=2,4,6-tris((dimethylamino)methyl)phenyl-]

The reactions of the divalent species (ArO)₂M (Ar=2,4,6-[(CH₃)₂NCH₂]₃C₆H₂; M=Ge, Sn) with either Me₃SiN₃, elemental S₈, Se or transition metal complexes M′(CO)_n+1 (M′=Fe, n=4; M′=Cr, W; n=5) (Ph₃P)₂Pt·C₂H₄ have resulted in the isolation of either the new stable formal metallanimines (ArO)₂M=N–SiMe₃, germanethione, -selone (ArO)₂Ge=E (E=S, Se) (the expected formations of the stannanethione and -selone were not observed), or the (ArO)₂M=M′(CO)_n, (ArO)₂M=Pt(PPh₃)₂ complexes, respectively. The direct oxidation of the (ArO)₂M species with various oxidizing agents led to the formation of the corresponding metalloxanes [(ArO)₂M–O–]₂. All of the chalcogenido- and transition metal–metal 14 complexes have been physicochemically and chemically characterized. The reactions of the (ArO)₂Ge=E (E=S, Se) compounds with 3,5-di-tert-butyl-1,2-benzoquinone produced, by extrusion of sulfur or selenium, the dioxametalloles corresponding to the formal addition of the divalent species (ArO)₂M to the benzoquinone. A substitution reaction of chalcogen (S/Se) has been observed permitting to go from germaneselone to germanethione.     

Transition-metal complexes of two valence tautomers of a bulky phenoxide, 2,6-Bu-t2-4-MeC6H2O− (ArO−); preparation and crystal and molecular structure of a phenoxytitanium(III) and a cyclohexadienonylrhodium(I) complex, [Ti(η-C5H5)2 OAr] and [Rh(ArO-η5)(PPh3)2]

The 2,6-di-t-butyl-4-methylphenoxo ligand (ArO^?) is ambidentate, giving rise to the O-bonded 15-electron d¹ [Ti(η-C₅H₅)₂OAr] and the η⁵ -[C(2)-C(6)]-bonded 18-electron d⁸ complex [Rh(ArO-η⁵)(PPh₃)₂], obtained from [{Ti(η-C₅H₅)₂Cl}₂]-LiO Ar and [Rh{N(SiMe₃)₂}(PPh₃)₂]-ArOH, respectively; the average TiC(η) distance is 2.362(10) Å, TiO 1.892(2) Å, and O:C(of Ar) 1.352(3) Å, and TiOC 142.3(2)°; in the Rh^I complex, C(2)C(6) are coplanar (with CC(av.) 1.38(2) Å). C(1)O 1.28 Å, and Rh to C(2) C(6) bond lengthsare in the range 2.19–2.65 Å.