Darstellung und NMR-spektroskopische Untersuchungen der tert-Butylimino-cyclopentadienylvanadium (V)-Verbindungen tC4H9NVCpX2 (X=SR,SeC6H5, Br,I)

Synthesis and NMR Spectroscopic Studies of tert-Butylimino-cyclopentadienylvanadium(V) Compounds ^tC₄H₉N?VCpX₂ (X=SR, SeC₆H₅, Br, I ) Syntheses of the cyclopentadienylvanadium(V) compounds ^tC₄H₉N?VCpX₂ (X=SR, SeC₆H₅, Br, I) ^tC₄H₉N?VCp (S^tC₄H₉) and ^tC₄H₉N?VCp[S? (CH₂)₃? S] ( 4 ) are described starting from ^tC₄H₉N?VCpCl₂. ^tC₄H₉N?VCl₃ reacts with BBr₃ and BI₃ by halogen exchange forming the trihalogenides ^tC₄H₉N?VX₃ (X=Br, I). All compounds obtained are characterized by ¹H and ⁵¹V NMR spectroscopy. 4 has been found by X-ray diffraction analysis to be a distorted tetrahedral vanadium complex with a chair conformation of the VS₂C₃-ring.     

Phosphan-, Phosphit- und Phosphido-Komplexe des Vanadiums(V)

Phosphane, Phosphite, Phosphido, Complexes of Vanadium(V) Complex formation of tert-butylimidovanadium(V)trichloride ( 1 ) with phosphanes und phosphites has been studied. Syntheses of phosphidovanadium(V) compounds ^tC₄H₉N?VCp(NH^tC₄H₉)[P(SiMe₃)₂] and ^tC₄H₉N?VCp(NⁱProp₂)(PR₂) (R?SiMe₃, Ph) are described starting from the corresponding chlorovanadium(V) complexes. The reaction of 1 with silver hexafluorophosphate yields a bis(fluoro)phosphidovanadium(IV complex [(μ-PF₂)₂V₂Cl₂)(N^tC₄H₉)₂]; as primary intermediate product of the unknown redox reaction a cationic vanadium(V) complex [^tC₄H₉N?VCl₂ · PPh₃]⁺PF₆^? has been isolated. 1 reacts with an excess of diisopropylamine forming ^tC₄H₉N?V(NⁱProp₂)Cl₂ ( 16 ); in addition the following diisopropylamido-tert-butylimidovanadium(V) compounds ^tC₄H₉N?VCp(NⁱProp₂)Cl ( 3 ) and ^tC₄H₉N?V(NⁱProp₂)X₂ (X?CH₂CMe₃, O^tC₄H₉, CH₃COO) has been prepared. All compounds obtained are characterized by ¹H, ⁵¹V, ³¹P NMR spectroscopy. The X-ray diffraction analysis of 16 and 3 indicate a planar coordination sphere of the amido nitrogen atom.     

1-D链状簇合物[Ni(enMe)_2]_2[Ni(enMe)_2{HMoo_4~(VI)Mo_4~V_8~(VI)VO_(40)(V~VO_4)}]·4H_2O的水热合成和晶体结构

水热合成了一种新的1-D链状四帽pseudo-Keggin 结构钼钒簇合物[Ni(enMe)2]2- [Ni(enMe)2{H MoVI4MoV4VIV8O40(VVO4)}]4H2O 1,X-射线单晶结构分析表明,该晶体属单斜晶系,C2/c空间群。晶体学参数为a = 26.3006(6), b = 13.6195(3), c = 19.7122(5) ,b = 105.8330(10), V = 6793.0(3) ?, Z = 4, Dc = 2.566 g/cm3, Mr = 2623.96, m = 3.507 mm-1, F(000) =5088, R = 0.0700, wR = 0.1529, S = 1.019。该簇合物是由金属配位桥Ni(enMe)2桥联四帽pseudo-Keggin 结构{HMoVI4MoV4VIV8O40(VVO4)}簇构成一维链状结构,链与链间通过与另外一个配位阳离子[Ni(enMe)2]2+的氢键相互作用构成超分子网状结构。     

新型杂多阴离子[{Na2(H2O)3}Ni(H2O)VOAs4W40O140]21-的结构及表征

在pH=4.5的水溶液中,Na27[NaAs4W40O140]·60H2O与NiCl2·6H2O, NaVO3·4H2O和NH4Cl反应得到了不同过渡金属离子占据S2位的新型杂多钨酸盐(NH4)21[{Na2(H2O)3}Ni(H2O)VOAs4W40O140]·53H2O,用X射线单晶衍射法和元素分析确定了其结构.晶胞参数为a=2.3305(14) nm, b=2.9467(19) nm, c=1.2671(16) nm, V=8.701(9) nm3, Z=2,空间群Pmmn.在杂多阴离子[{Na2(H2O)3}Ni(H2O)VOAs4W40O140]21-中,配体{As4W40}的1个中心位和4个S2位可以选择性地被不同的金属离子所占据,其中相对的2个S2位被Ni2+和V5+统计性地占据,每种离子占据的概率为50%;{As4W40}中的另2个S2位分别被2个Na+占据,2个Na+间通过一配位水分子桥连.讨论了标题化合物的IR, TG和磁学性质.     

Synthesis and Crystal Structure of [H-amp]4[Mo8O26（DMF）2].2H2O（amp = 2-Amino-6-methyl-pyridine）

1INTRODUCTIONMetal-oxoclusterchemistryhasbeenactivelypurchasedduetotheinterestinchemistryitselfanditsvariousapplicationsinfieldssuchascatalysis,electronicconductivity,magnetism,nonlinearopti-calpropertiesandmedicine[1～3].Recently,anim-portantadvanceinmet…     

Synthesis and Crystal Structure of [H-amp]4[Mo8O26(DMF)2]·2H2O (amp = 2-Amino-6-methyl-pyridine)

The reaction of MoO2(acac)2 with 2-amino-6-methyl-pyridine (amp) in the mixed solvent of DMF (N,N-dimethylformamide) and water affords the title complex [H-amp]4- [Mo8O26(DMF)2]·2H2O which was characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction analysis with the following crystallographic data: C30H54Mo8N10O30, Mr = 1802.35, monoclinic, P21/n, a = 8.631(1), b = 24.260(3), c = 13.351(2)A,β= 104.688(3)°, V = 2704.2(7) A3, Z = 2, Dc = 2.213 g/cm3, μ =1.890 mm－1 and F(000) = 1760. The final R = 0.0281 and Wr = 0.0620 for 4935 observed reflections with I > 2σ(I). X-ray structure analysis has confirmed the existence of γ-[Mo8O26]4－ anion in the molecule. Eight MoO6 distorted octahedra share edges with short terminal Mo-O bonds from 1.691(3) to 1.749(2)A, medium bonds from 1.868(2) to 1.965(2) A And long bonds from 2.059(2) to 2.450(2) A. In the terminal site there exist two DMF ligands bound to the Mo atom through O atoms with the Mo-ODMF bond length of 2.166(3) A, affording a bond strength of 0.433. A three-dimensional network structure was formed through hydrogen bonds.     

Darstellung und Struktur der Zweikernigen tert-Butyliminovanadium(IV)-Komplexe [(μ?NtC4H9)2V2(CH2CMe3)2X2] (X = OtC4H9, CH2CMe3)

Synthesis and Molecular Structure of the Binuclear tert-Butyliminovanadium(IV) Complexes [(μ-N^tC₄H₉)₂V₂(CH₂CMe₃)₂X₂] (X = O^tC₄H₉, CH₂CMe₃) Syntheses of the neopentylvanadium(V) compounds ^tC₄H₉N?V(CH₂CMe₃)_3?n(O^tC₄H₉)_n (n = 0 ( 7 ), 1 ( 6 ), 2) are described. 6 and 7 decompose by irradiation splitting off neopentane and yielding the binuclear diamagnetic neopentylvanadium(IV) complexes [(μ-N^tC₄H₉)₂V₂(CH₂CMe₃)₂X₂] [X = O^tC₄H₉ ( 8 ), CH₂CMe₃ ( 11 )]. All compounds obtained are characterized by ¹H and ⁵¹V NMR spectroscopy. 8 has been found by X-ray diffraction analysis to be a binuclear complex with bridging tert-butylimino ligands and a vanadium—vanadium single bond. The complexes ^tC₄H₉N?V(CH₂C₆H₅)(O^tC₄H₉)₂ and [(μ-N^tC₄H₉)₂V₂(CH₂SiMe₃)₂(O^tC₄H₉)₂] ( 10 ) have been also prepared; the crystal structure of 8 and 10 are nearly identical.     

[Cu(enMe)_2]_4[H_5V_(18)~(IV)O_(42)(Cl)]·8H_2O:由金属-氧簇和金属配合物构筑的微孔材料的合成和结构

合成了标题化合物[Cu(enMe)2]4[H5VIV18O42(Cl)]8H2O 1,晶体属于四方晶系,P4/nnc空间群,晶胞参数a = 15.0034(3), c = 18.8149(3) ? V = 4235.27(14) ?, Z = 2, Dc = 2.055 g/cm3, Mr = 2620.74, m = 2.988 mm-1, F(000) = 2608, R = 0.0766, wR = 0.2118, S = 1.193, (Δr)max = 0.969×103 , (Δr)min = 0.454×103 e/3。化合物1的阴离子[VIV18O42(Cl)]8-通过金属配合物阳离子[Cu(enMe)2]2+连接形成3-D骨架结构。     

含有两个簇阴离子[As8V14O42(SO4)]6-的金属-氧簇合物(H2en)6[As8V14O42(SO4)]2(8H2O的水热合成与晶体结构

合成了一种新的砷-钒-氧簇合物(H2en)6[As8V14O42(SO4)]28H2O(en为乙二胺),用元素分析、IR和TG-DTA等手段进行了表征,并用X射线衍射法测定了晶体结构。结果表明, 该晶体属单斜晶系,P21/c空间群,晶胞参数a = 20.9235(4),b = 11.9382(2),c = 43.5783(6) 牛琤 = 102.13,V = 10642.1(3) ?,Z = 4,Mr = 4678.01,Dc = 2.920 g/cm3,F(000) = 8944,m = 7.437 mm-1,R = 0.0735,wR = 0.1361。结构测定表明,结构中2个簇阴离子{[As8V14O42(SO4)]6-}与有机铵阳离子[H2en]2+之间靠静电作用相结合,同时与H2O通过氢键构成无限的三维骨架结构。     

二个含水杨酰腙配体的钒配合物的合成与晶体结构研究

2种水杨酰腙配体H2L1(H2L1=邻羟基苯乙酮缩水杨酰腙)和H2L2(H2L2=水杨醛缩水杨酰腙)分别与VO(acac)2反应,合成了2个钒配合物[VOL1(C2H5O)]2(1)和[VOL2(i-C3H7O)](2),利用元素分析、红外光谱、紫外光谱和单晶衍射等手段进行表征。配合物1是由酚氧原子桥联2个金属中心形成的具有晶体学中心对称性的双核钒(V)配合物结构,每个V(V)原子具有扭曲的八面体配位构型。配合物2为单核结构,每个V(V)原子具有扭曲的四角锥配位构型,相邻的配合物分子通过分子间氢键作用形成一维超分子链状结构。采用循环伏安法研究了化合物2的电化学性质。     

Multinuclear magnetic resonance study of some imidovanadium complexes

¹⁴N NMR studies were carried out for a series of mononuclear and dinuclear vanadium complexes with different types of nitrogen ligands (terminal and µ‐imido, amido, nitrido, amine). Some complexes containing ancillary phosphine moieties were also characterized by ³¹P NMR spectroscopy. The observed shieldings for terminal and bridging imido ligands are intermediate between those of nitrido and amido moieties, and the latter appear less shielded than coordinated tertiary amines. The ranges for individual ligand types are sufficiently resolved to allow the use of nitrogen chemical shifts as a structure assignment tool. The ¹⁴N NMR signals of terminal and bridging imido nitrogens displayed marked differences in their lineshapes which could be used as an additional criterion for signal assignment. Examination of substituent influences revealed the absence of a general parallelism between δ¹⁴N and δ⁵¹V, but gave evidence for parallel relationships between both quantities for complexes with formal 12VE and 16VE electron counts. Determination of ¹J(⁵¹V,¹⁴N) and ¹J(⁵¹V,³¹P) coupling constants in mononuclear complexes was feasible from simulation of ¹⁴N and ³¹P lineshapes and suggested that imido ligands exhibit generally greater couplings to vanadium than amido ligands. Analysis of the ³¹P {¹H,¹⁴N} NMR spectrum allowed us to determine ²J(⁵¹V,³¹P) for the vanadacycle cyclo(^tBuN—P?C(^tBu)—VCl₃—). It was shown that both couplings can be employed for the acquisition of two‐dimensional ³¹P,⁵¹V shift correlations. Copyright © 2001 John Wiley & Sons, Ltd.     

Komplexbildung des tert-Butyliminovanadium(V)-trichlorids mit O-Donor-Liganden

Coordination Compounds of tert-Butyliminovanadium(V) Trichloride with O-Donor-Ligands The reaction of tert-butyliminovanadium(V)trichloride ( 1 ) with cyclic and acyclic ethers, ethylene carbonate and thietane has been studied. The 1:1-complexes have a different stability; reversible and irreversible cleavage of ether in the coordination sphere of the vanadium atom rearranging in ω-chloroalkanolato ligands are observed. The reaction of 1 with 2-chloroethanol, 3-chloropropanol and 5-chloropentanol yields the complexes ^tC₄H₉N = V(OR)Cl₂ (R = CH₂CH₂CH₂CH₂CH₂Cl) and [^tC₄H₉N = V(OR)Cl₂ · ROH]; in the presence of triethylamine the disubstituted compounds ^tC₄H₉N = V(OR)₂Cl are formed. The ⁵¹V NMR spectra are discussed. The crystal structure of [^tC₄H₉N = VCl₃ · DME] ( 12 ) and [^tC₄H₉N = V(OCH₂CH₂Cl)Cl₂ · HOCH₂CH₂Cl] ( 13 ) has been determined. The vanadium atoms in 13 have a distorted octahedral coordination and are linked by the oxygen atoms of the 2-chloroethanolato ligands forming a binuclear complex. In solution molecular weight measurement and ⁵¹V NMR data indicate the equilibrium between a mononuclear complex 13 and its isomer [^tC₄H₉N = V(OCH₂CH₂Cl)₂Cl · HCl].     

The Missing Link in Low Nuclearity Pure Polyoxovanadate Clusters: Preliminary Synthesis and Structural Analysis of a New {V16} Cluster and Related Products

Two new metastable polyoxovanadate-based cluster compounds have been isolated and crystallographically characterized with nuclearities of {V₁₆} (1) and {V₁₈} (2). The {V₁₆} cluster represents a new framework type and incorporates two protons into the cluster framework whereas the {V₁₈} framework has been previously characterised, and the oxidation states of the {V₁₈} cluster can be assigned as {V^IV ₁₅V^V ₃}. Compound K₁₀[H₂V₁₆O₃₈]13H₂O (1) crystallizes in the monoclinic space group P2₁/c, a=12.12820(10), b=38.2302(3), c=12.35400(10) Å, =115.0470(10)°, V=5189.43(7) ų, D _c=2.624 gcm^–3. 10086 unique reflection and 702 refined parameters were used in structure refinement. R1=0.039, R2=0.109 (all data). From the same preparation the new compound K₁₁[V₁₈O₄₂(SO₄)]20H₂O (2) was also isolated and crystallographically characterized. Compound 2 crystallizes in the monoclinic space group P2₁/n, a=12.7854(3), b=20.2812(5), c=13.2386(4) Å, =115.3400(10)°, V=3102.53(14) ų, D _c=2.650 gcm^–3. 7115 unique reflections and 462 refined parameters were used in structure refinement. R1=0.046, R2=0.121 (all data).     

Hydrothermal Assembly and Structural Characterization of an Octamolybdate Supported Copper (Ⅰ) Tetramer: [Cu_2(1,10-phen)_2(4,4′-bpy)]_2[Mo_8O_(26)]·4H_2O

1 INTRODUCTION The recent expansion of the field of heteropolyoxometalate chemistry derives from their vast topological structures and applicable physical properties[1～5]. One of the crucial strategies for the molecular design of solid materials is how to apply hydrothermal synthesis method to introduce some interesting transition metal coordinated fragments into the covalent backbones of solid materials. Studies have been focused on organic-inorganic hybrid materials containing one kin…     

Hydrothermal Assembly and Structural Characterization of an Octamolybdate Supported Copper(Ⅰ) Tetramer:[Cu2(1,10-phen)2(4,4'-bpy)]2[Mo8O26]·4H2O

A hydrothermal reaction of copper acetate with ammonium molybdate, 4,4'-bpy (4,4'-bipyridine) and 1,10-phen (1,10-phenanthroline) led to the formation of brown crystals of [Cu2(1,10-phen)2(4,4'-bpy)]2 [Mo8O26]@4H2O 1. Single-crystal X-ray analysis has revealed that 1 C68H56N12O30Cu4Mo8 crystallizes in the triclinic system, space group P ī with a = 11.270(3), b = 13.113(6), c = 13.906(3)A, α = 103.33(4),α = 98.54(2),β= 101.29(2)°, V = 1920.1(1)A3, Mr = 2542.9(3), Z = 1, Dc = 2.199 g/cm3, μ= 2.435 mm-1, F(000)= 1240, the final R = 0.0445, wR = 0.1082 and S = 1.021 for 5052 observed reflections with I>σ2(I).It consists of copper Ⅰ tetramer units and α-[Mo8O26]4- anions, which are further attached into a three-dimensional framework through hydrogen bonding and π-π stacking interactions.     

Hydrothermal Synthesis and Crystal Structure of a Hybrid Compound Based on β-Octamolybdate [Mn(2,2’-bipy)_3]_2[β-Mo_8O_(26)]·4H_2O

1 INTRODUCTION Polyoxometalates (POMs) are one of the most widely used inorganic components due to their at- tractive electronic and molecular properties with va- rious applications in catalysis, medicine, materials science[1～3] and so on. Exploration of transition me- tal complex cations as well as organic component which functions as ligand as building blocks in the construction of metal oxide composite materials is a fruitful strategy[4, 5]. Among the polyoxometalates studied to dat…     

Syntheses,Structures, and Reactivities of Sulfur-Containing Cycloalkenes

Sulfur-containing cycloalkenes possessing disulfide units 1, 2, and 3 were obtained by oxidation of cis-disodium ethene-1,2-dithiolate, and their crystal structures were determined by the X-ray crystallographic analyses. Compound 1 was found to give the ring expansion product 3 in acetonitrile even at room temperature and also form reactive thioaldehyde under irradiation.