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1.
Indium(III) chloride forms in water with potassium 1,2‐dithiooxalate (dto) and potassium 1,2‐dithiosquarate (dtsq) stable coordination compounds. Due to the higher bridging ability of the 1,2‐dithiooxalate ligand in all cases only thiooxalate bridged binuclear complexes were found. From 1,2‐dithioquadratate with an identical donor atom set mononuclear trischelates could be isolated. Five crystalline complexes, (BzlMe3N)4[(dto)2In(dto)In(dto)2] ( 1 ), (BzlPh3P)4[(dto)2In(dto)In(dto)2] ( 2 ), (BzlMe3N)3[In(dtsq)3] ( 3 ), (Bu4N)3[In(dtsq)3] ( 4 ) and (Ph4P)[In(dtsq)2(DMF)2] ( 5 ), have been isolated and characterized by X‐ray analyses. Due to the type of the complex and the cations involved these compounds crystallize in different space groups with the following parameters: 1 , monoclinic in P21/c with a = 14.4035(5) Å, b = 10.8141(5) Å, c = 23.3698(9) Å, β = 124.664(2)°, and Z = 2; 2 , triclinic in P with a = 11.3872(7) Å, b = 13.6669(9) Å, c = 17.4296(10) Å, α = 88.883(5)°, β = 96.763(1)°, γ = 74.587(5)°, and Z = 1; 3 , hexagonal in R3 with a = 20.6501(16) Å, b = 20.6501(16) Å, c = 19.0706(13) Å and Z = 6; 4 , monoclinic in P21/c with a = 22.7650(15) Å, b = 20.4656(10) Å, c = 14.4770(9) Å, β = 101.095(5)°, and Z = 4; 5 , triclinic in P with a = 9.2227(6) Å, b = 15.3876(9) Å, c = 15.5298(9) Å, α = 110.526(1)°, β = 100.138(1)°, γ = 101.003(1)°, and Z = 2.  相似文献   

2.
Nickel(I) Complexes with 1,1′‐Bis(phosphino)ferrocenes as Ligands The thermically stable monomeric Nickel(I) complexes [(dtbpf)Ni(acac)] ( 1 ) and [(dippf)NiCl] ( 2 ) were synthesized and characterized by elemental analyses, EPR spectroscopy, and by X‐ray crystal structure analyses of single crystals (dtbpf: 1,1′‐bis(di‐tertbutylphosphino)ferrocene; dippf: 1,1′‐bis(diisopropylphosphino)ferrocene). 1 is formed by reduction of Ni(acac)2 with triethylaluminium in the presence of dtbpf, together with the nickel(0) complex [(dtbpf)Ni(C2H4)]. 1 contains a NiI atom surrounded of two O‐ and two P donor atoms in a distorted tetrahedral coordination. 2 was obtained by reduction of [(dippf)NiCl2] with NaBH4. In 2 the nickel(I) atom adopts trigonal planar coordination.  相似文献   

3.
Structural Interactions of Planar and Non‐planar Bis(1,2‐dithiosquarato)metalate Host Lattices with CuII Complexes – Structure and EPR Investigations 1,2‐Dithiosquaratometalates (M = Cu, Ni, Zn) are available by direct synthesis from metal salts with dipotassium‐1,2‐dithiosquarate. The structural influence of the planar and nonplanar host lattice systems (BzlEt3N)2[Cu/Ni(dtsq)2] and (BzlEt3N)2[Cu/Zn(dtsq)2] on the geometrical and electronic structure of the CuII guest complex [Cu(dtsq)2]2– is studied by EPR spectroscopy. The used host lattices (BzlEt3N)2[Ni(dtsq)2] (planar) and (BzlEt3N)2[Zn(dtsq)2] (tetrahedral) are characterized by X‐ray structure analysis. (BzlEt3N)2[Ni(dtsq)2] crystallizes in the triclinic unit cell P1 with a = 9.1021(8) Å, b = 9.4190(8) Å, c = 11.0119(10) Å, α = 92.8560(10)°, β = 95.375(2)°, γ = 104.5180(10)° and Z = 1. (BzlEt3N)2[Zn(dtsq)2] crystallizes in the monoclinic unit cell C2/c with a = 21.1299(14) Å, b = 16.6641(11) Å, c = 13.8324(9) Å, β = 123.9100(10)° and Z = 4. The g and A Cu tensors in the Cu/Ni system are nearly axial symmetric (g|| = 2.122, g = 2.028; A = –159.5 · 10–4 cm–1, A = –36.9 · 10–4 cm–1). The coordination geometry of the CuII guest complex in the tetrahedral Cu/Zn system is rather distorted, which is shown by the changed g and A Cu tensor parameters (g|| = 2.143, g = 2.042; A = –103.0 · 10–4 cm–1, A ≈ –5.0 · 10–4 cm–1). The spin density distribution is discussed using EHT molecular orbital calculations.  相似文献   

4.
A novel two‐dimensional cobalt complex, [Co(btrm)2(dca)]ClO4 ( 1 , btrm = 1,2‐bis(1,2,4‐triazole‐1‐yl)methane, dca = dicyanamide), was synthesized and characterized. X‐ray diffraction analyses reveal that the title complex crystallizes in the monoclinic space group C2/m with a = 29.507(13)Å, b = 17.804(8) Å, c = 14.709(7) Å, β = 119.916(7)°, Z = 12, and R1 = 0.0784, wR2 = 0.2041. The cobalt atom involves a six‐coordinated CoN6 environment, with a distorted octahedral coordination. Two btrm ligands connect the CoII atoms with the exodentate nitrogen atoms on the 4‐position of triazole rings to form a sixteen‐membered rhombic grid. The unprecedented double btrm bridges and μ1,5‐dca bridge connect the cobalt atoms to form a two‐dimensional grid‐like layered structure. The spectroscopic and magnetic properties have also been investigated.  相似文献   

5.
The salen‐type ligand H2L [H2L = N,N′‐bis(salicylidene)‐1,2‐cyclohexanediamine] was utilized for the synthesis of two lanthanide(III) coordination polymers [LnH2L(NO3)3MeOH]n [Ln = Eu ( 1 ) and Ln = Lu ( 2 )]. The single‐crystal X‐ray diffraction analyses of 1 and 2 revealed that they are isomorphous and exhibit one‐dimension neutral structure, in which H2L effectively functions as a bridging ligand and give rise to a chain‐like polymer. The luminescent properties of polymers in solid state and in solution were investigated and 1 exhibits typical red luminescence of EuIII ions in solid state and dichloromethane solution and 2 emits the ligand‐centered blue luminescence. The energy transfer mechanisms in these luminescent lanthanide polymers were described through calculation of the lowest triplet level of ligand H2L.  相似文献   

6.
A convenient method for the preparation of diphenylboron chelates from ammonium tetraphenylborate is described. A variety of five‐ or six‐membered O,O‐, N,O‐ and N,N‐chelates were obtained in yields from 60 to 90 %. The isolated compounds were characterized by elemental analysis, IR spectroscopy and multinuclear magnetic resonance spectroscopy (1H, 13C, and 11B). The crystal and molecular structures of (pyridine‐2‐acetyloximato)diphenylboron and (1‐phenylazo‐2‐naphtholato)diphenylboron were determined by X‐ray diffraction on single crystals.  相似文献   

7.
Polymorphism of Bis(dineopentoxyphosphorothioyl)diselenide – Correlation of X‐Ray Structure and MAS NMR Data The crystal structures of two polymorphs of the title compound were determined by single‐crystal X‐ray methods and refined both at room temperature and 250 K. A triclinic and a monoclinic phase were discovered and studied. Both modifications are centrosymmetrical layer structures. The numerically clearly significant differences were observed in unit cell volumes as well as in alternating disproportions of distances of atoms being chemically and crystallographically equivalent as a result of discontinuously distributed conformational changes along the single bonds. Phase transitions were not observed by cooling up to 240 K. Lowering temperatures single crystals of both phases decompose because of the considerable anisotropy of intermolecular interaction. The small differences of molecular structure produce slightly splitted 31P CP MAS NMR signals. A comparison of the chemical shifts from 13C CP MAS NMR spectra and from quantum‐chemical calculations leads to the conclusion that the inner rotation around CH2–Cq bonds is not frozen in the solid state.  相似文献   

8.
(E)‐ and (Z)‐1,2‐bis(trifluoromethyl)ethene‐1,2‐dicarbonitrile ((E)‐ and (Z)‐BTE, resp., =(E)‐ and (Z)‐2,3‐bis(trifluoromethyl)but‐2‐enedinitrile) were used as a stereochemical probe in studying (2+2) cycloadditions of acceptor with donor alkenes. The additions to methyl (E)‐ and (Z)‐propenyl ether gave rise to the eight conceivable cyclobutanes 8 , although in different ratios in reactions of (E)‐ and (Z)‐BTE. The 19F‐NMR data served the structural assignment and the quantitative analysis. The mechanistic discussion is based on rotations and ring closures of the assumed 1,4‐zwitterionic intermediates. Dimethylketene dimethyl acetal, methylketene dimethyl acetal, and ketene diethyl acetal show an increasing rate in their reactions with BTE as well as in the equilibration of the cycloadducts.  相似文献   

9.
Syntheses and NMR Spectroscopic Ivestigations of Salts containing the Novel Anions [PtXn(CF3)6‐n]2— (n = 0 ‐ 5, X = F, OH, Cl, CN) and Crystal Structure of K2[(CF3)2F2Pt(μ‐OH)2PtF2(CF3)2]·2H2O The first syntheses of trifluoromethyl‐complexes of platinum through fluorination of cyanoplatinates are reported. The fluorination of tetracyanoplatinates(II), K2[Pt(CN)4], and hexacyanoplatinates(IV), K2[Pt(CN)6], with ClF in anhydrous HF leads after working up of the products to K2[(CF3)2F2Pt(μ‐OH)2PtF2(CF3)2]·2H2O. The structure of the salt is determined by a X‐ray structure analysis, P21/c (Nr. 14), a = 11.391(2), b = 11.565(2), c = 13.391(3)Å, β = 90.32(3)°, Z = 4, R1 = 0.0326 (I > 2σ(I)). The reaction of [Bu4N]2[Pt(CN)4] with ClF in CH2Cl2 generates mainly cis‐[Bu4N]2[PtCl2(CF3)4] and fac‐[Bu4N]2[PtCl3(CF3)3], but in contrast that of [Bu4N]2[Pt(CN)6] with ClF in CH2Cl2 results cis‐[Bu4N]2[PtX2(CF3)4], [Bu4N]2[PtX(CF3)5] (X = F, Cl) and [Bu4N]2[Pt(CF3)6]. In the products [Bu4N]2[PtXn(CF3)6‐n] (X = F, Cl, n = 0—3) it is possibel to exchange the fluoro‐ligands into chloro‐ and cyano‐ligands by treatment with (CH3)3SiCl und (CH3)3SiCN at 50 °C. With continuing warming the trifluoromethyl‐ligands are exchanged by chloro‐ and cyano‐ligands, while as intermediates CF2Cl and CF2CN ligands are formed. The identity of the new trifluoromethyl‐platinates is proved by 195Pt‐ and 19F‐NMR‐spectroscopy.  相似文献   

10.
Tetrakis(1‐adamantylcarboxylato)dicopper(II) Cu2(1‐Ad)4 – Synthesis, Structure and X‐/Q‐band EPR Investigations The synthesis and the crystal structure of tetrakis(1‐adamantylcarboxylato)dicopper(II) are reported. [Cu2(1‐Ad)4·2DMF] ( 1 , 1‐Ad = adamantylcarboxylate) crystallizes in the space group (Z = 2) with two crystallographically distinguishable complexes in the unit cell. The averaged Cu‐Cu distance of 260.5 pm is smaller than that found for Cu2(ac)4·2H2O. The combination of temperature‐dependent X‐ and Q‐band powder EPR investigations in the temperature range 6 ≤ T ≤ 295 K show the presence of an antiferromagnetically coupled Cu‐Cu dimer and allow a precise determination of the spin‐Hamiltonian parameter. A comparison of those with that derived for Cu2(ac)4·2H2O indicate a higher symmetry within the Cu2O8 central unit of [Cu2(1‐Ad)4·2DMF].  相似文献   

11.
Three new coordination polymers, [Zn(PBDC)(bbbm)0.5]n ( 1 ), [Co(PBDC)(bbbm)]n ( 2 ), and [Cd(PBDC)(bbbm)]n ( 3 ) were prepared via hydrothermal reactions of different metal(II) nitrates with flexible 1,3‐bis(4‐phenoxy)benzenedicarboxylic acid (H2L) and 1,1‐(1,4‐butanediyl)bis(benzimidazole) ligand. All these complexes were fully characterized by elemental analysis, FT‐IR, thermogravimetric analysis (TGA), powder X‐ray diffraction, and single‐crystal X‐ray diffraction. Structure analyses revealed that complex 1 has a 2D→2D twofold interpenetrating framework simplified by a 4‐connected sql net with point symbol (44.62), whereas complexes 2 and 3 are isostructural and exhibit a 2D→2D twofold interpenetrating framework rationalized as a three‐connected hcb net with point symbol (63). Complexes 1 – 3 further expand to 3D supramolecular structures through non‐covalent C–H ··· O interactions. Additionally, the luminescent and magnetic properties of some of these complexes were studied. Complex 3 presents ideal photoluminescent behavior, whereas complex 2 shows antiferromagnetic coupling between the central CoII ions, suggesting its latent application in magnetic material.  相似文献   

12.
A new mercury(II) complex of 1,2‐bis(4‐pyridyle)ethene (bpe) with anionic acetate and thiocyanate ligands has been synthesized and characterized by elemental analysis, IR, 1H NMR and 13C NMR spectroscopy. The single crystal X‐ray analysis shows that the complex is a two‐dimensional polymer with simultaneously bridging 1,2‐bis(4‐pyridyle)ethane, acetate and thiocyanate ligands and basic repeating dimeric [Hg2(μ‐bpe)(μ‐OAc)2(μ‐SCN)2] units. The two‐dimensional system forms a three‐dimensional network by packing via ππ stacking interactions.  相似文献   

13.
Turquoise monoclinic single crystals of the novel three‐dimensional Cu28‐O3P(CH2)2PO3] · 3.2H2O coordination polymer were prepared using the silica gel method. Space group C2/m (no. 12) with a = 1483.6(2), b = 668.44(8), c = 436.30(6) pm, β = 93.28(2)°. The Cu2+ cation is coordinated by four oxygen atoms stemming from the 1,2‐ethylenediphosphonate dianions in a square planar manner and two water molecules in the axial positions. The connection between the Cu2+ cations and the [CPO3] units from the 1,2‐ethylenediphosphonate dianions leads to layers parallel to (100), which are linked by the ethylene groups to a three‐dimensional framework with channel‐like voids. The channel‐like voids accommodate water molecules not bound to Cu2+ and extend parallel to [001] with an opening of about 550 pm × 260 pm. Magnetic measurements reveal an antiferromagnetic behavior due to a superexchange coupling between Cu2+ ions through an oxygen bridge. The UV/Vis spectrum reveals three d–d transition bands at 694, 774, and 918 nm. The compound can be fully dehydrated by thermal treatment and rehydrated by storage in ambient air.  相似文献   

14.
The new ligand bis(4‐pyridylthio)methane (4‐bpytm) ( 1 ) and its complexes [CuX2(4‐bpytm)] and [CuX2(4‐bpytm)2] (X = Cl and Br) ( 2 – 5 ) have been prepared and characterized by elemental analysis, IR‐Raman, UV/Vis spectroscopy. The structures of (4‐bpytm) ( 1 ), [CuCl2(4‐bpytm)2] ( 3 ) and [CuBr2(4‐bpytm)2] ( 4 ) were determined by single‐crystal X‐ray diffraction analysis. X‐ray analysis of the 1:2 derivatives reveals that the copper atom has a distorted (4 + 2) octahedral environment. The copper atom is coordinated by four nitrogen atoms from four bridging 4‐bpytm ligands and two halogen atoms. The axial Cu–N bonds are considerably longer than the equatorial Cu–N bonds owing to JahñTeller distortion. CuX2 units are linked to each other through bridging 4‐bpytm ligands to form a 2D interpenetrated coordination polymer. The structural parameters of the 4‐bpytm ligand in these complexes were compared with those of the free ligand.  相似文献   

15.
16.
Pale‐green crystals of the title complex were prepared by reaction of 2‐formylpyridine semicarbazone (HCSpy) and nickel(II) perchlorate in boiling ethanol. The crystals are triclinic with the nickel ion in an octahedral arrangement, coordinated by two nitrogen atoms and one oxygen donor atom from each ligand molecule. The effect of coordination on bond lengths and angles was explored by comparison with the single‐crystal structure data of the free ligand HSCpy, which was collected as well. The assumed coordination mode was supported by 1H and 13C NMR spectroscopic data. A detailed analysis of the electronic properties, including semi‐empirical quantummechanical calculations is presented. Furthermore, the data obtained from magnetic susceptibility and EPR measurements are in accordance with a low‐spin d8 nickel(II) complex.  相似文献   

17.
Abstract. Two coordination polymers, namely, [Zn(bpe)0.5(Htbip)(tbip)0.5] · H2O ( 1 ) and [Cd(bpe)0.5(tbip)] ( 2 ) [H2tbip = 5‐tert‐butylisophthalic acid and bpe = 1, 2‐ bis(4‐pyridyl) ethane] were synthesized through hydrothermal reactions. Single‐crystal X‐ray diffraction analysis reveals that complex 1 presents a three‐dimensional (3D) six‐connected uninodal structure with the type of topology of svi‐x/I4/mcmIbam, whereas complex 2 holds a 2D 44sql layer structure. Moreover, the photoluminescent properties of the complexes at room temperature were investigated.  相似文献   

18.
(E) and (Z)‐1,2‐bis(trifluoromethyl)ethene‐1,2‐dicarbonitrile (BTE; (=E) and (Z)‐1,2‐bis(trifluoromethyl)but‐2‐enedinitrile) were reacted with an excess of methyl vinyl ether, used as solvent, and furnished 1 : 2 adducts 6 (54%) and cyclobutanes 3 as 1 : 1 adducts (41%). The four diastereoisomeric bis‐adducts 6 (different ratios from (E) and (Z)‐BTE) are derivatives of 1‐azabicyclo[4.2.0]oct‐5‐ene; X‐ray analyses and 19F‐NMR spectra revealed their structures. Since the cyclobutanes 3 are resistant to vinyl ether, the pathways leading to mono‐ and bis‐adducts must compete on the level of the intermediate l,4‐zwitterions 1 and 2 . The latter either cyclize to the cyclobutanes 3 or to six‐membered cyclic ketene imines 8 which accept a second molecule of vinyl ether to yield the bis‐adducts 6 . The occurrence of the highly strained ketene imines 8 gains credibility by comparison to stable seven‐membered cyclic ketene imines recently reported.  相似文献   

19.
Synthesis of Dimethoxyethane and Tetrahydrofuran Complexes of Rare‐Earth Nitrates – Solid State Structure of Pr(NO3)3(thf)4 The solvated rare‐earth nitrates Ln(NO3)3(thf)n (Ln = Pr, n = 4 ( 1 ); Ln = Ho ( 2 ), Yb ( 3 ), n = 3 and Ln(NO3)3(dme)2; Ln = Pr ( 4 ), Ho ( 5 )) were obtained from Ln(NO3)3(H2O)x and HC(OCH3)3. Pale green thermally labile crystals of 1 were characterized by X‐ray crystallography. The praseodymium atoms in two independent monomeric molecules show capped trigonal prismatic and pentagonal bipyramidal coordination, respectively.  相似文献   

20.
Three dinuclear copper(I) complexes, [Cu2(µ‐Cl)2(1,2‐(PPh2)2‐1,2‐C2B10H10)2]·2CH2Cl2 ( 1 ), [Cu2(µ‐Br)2(1,2‐(PPh2)2‐1,2‐C2B10H10)2]·2THF ( 2 ) and {Cu2(µ‐I)2[1,2‐(PPh2)2‐1,2‐C2B10H10]2} ( 3 ) have been synthesized by the reactions of CuX (X = Cl, Br and I) with the closo ligand 1,2‐(PPh2)2‐1,2‐C2B10H10. All these complexes were characterized by elemental analysis, FT‐IR, 1H and 13C NMR spectroscopy and X‐ray structure determination. Single crystal X‐ray structure determinations show that every complex contained di‐µ‐X‐bridged structure involving a crossed parallelogram plane formed by two Cu atoms and two X atoms (X = Cl, Br, I). The geometry at the Cu atom was a distorted tetrahedron, in which two positions were occupied by two P atoms of the PPh2 groups connected to the two C atoms of carborane (Cc), and the other two resulted from two X atoms which bridged the other Cu atom at the same time. To the best of our knowledge, this is the first example of copper(I) complexes with 1,2‐diphenylphosphino‐1,2‐dicarba‐closo‐dodecaborane as ligand characterized by X‐ray diffraction. The catalytic property of the complex 3 for the amination of iodobenzene with aniline was also investigated. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

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