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1.
Takashi Tamaki Midue Nagata Masato Ohashi Dr. Sensuke Ogoshi Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(39):10083-10091
Cyclopropanecarboxaldehyde ( 1 a ), cyclopropyl methyl ketone ( 1 b ), and cyclopropyl phenyl ketone ( 1 c ) were reacted with [Ni(cod)2] (cod=1,5‐cyclooctadiene) and PBu3 at 100 °C to give η2‐enonenickel complexes ( 2 a – c ). In the presence of PCy3 (Cy=cyclohexyl), 1 a and 1 b reacted with [Ni(cod)2] to give the corresponding μ‐η2:η1‐enonenickel complexes ( 3 a , 3 b ). However, the reaction of 1 c under the same reaction conditions gave a mixture of 3 c and cyclopentane derivatives ( 4 c , 4 c′ ), that is, a [3+2] cycloaddition product of 1 c with (E)‐1‐phenylbut‐2‐en‐1‐one, an isomer of 1 c . In the presence of a catalytic amount of [Ni(cod)2] and PCy3, [3+2] homo‐cycloaddition proceeded to give a mixture of 4 c (76 %) and 4 c′ (17 %). At room temperature, a possible intermediate, 6 c , was observed and isolated by reprecipitation at ?20 °C. In the presence of 1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene (IPr), both 1 a and 1 c rapidly underwent oxidative addition to nickel(0) to give the corresponding six‐membered oxa‐nickelacycles ( 6 ai , 6 ci ). On the other hand, 1 b reacted with nickel(0) to give the corresponding μ‐η2:η1‐enonenickel complex ( 3 bi ). The molecular structures of 6 ai and 6 ci were confirmed by X‐ray crystallography. The molecular structure of 6 ai shows a dimeric η1‐nickelenolate structure. However, the molecular structure of 6 ci shows a monomeric η1‐nickelenolate structure, and the nickel(II) 14‐electron center is regarded as having “an unusual T‐shaped planar” coordination geometry. The insertion of enones into monomeric η1‐nickelenolate complexes 6 c and 6 ci occurred at room temperature to generate η3‐oxa‐allylnickel complexes ( 8 , 9 ), whereas insertion into dimeric η1‐nickelenolate complex 6 ai did not take place. The diastereoselectivity of the insertion of an enone into 6 c having PCy3 as a ligand differs from that into 6 ci having IPr as a ligand. In addition, the stereochemistry of η3‐oxa‐allylnickel complexes having IPr as a ligand is retained during reductive elimination to yield the corresponding [3+2] cycloaddition product, which is consistent with the diastereoselectivity observed in Ni0/IPr‐catalyzed [3+2] cycloaddition reactions of cyclopropyl ketones with enones. In contrast, reductive elimination from the η3‐oxa‐allylnickel having PCy3 as a ligand proceeds with inversion of stereochemistry. This is probably due to rapid isomerization between syn and anti isomers prior to reductive elimination. 相似文献
2.
两种镍的配合物[Ni(NH2CH2CH2CH2NH2)3]Cl2 (1)和[Ni(C6H4N2H4)2Cl2] (2)已经被合成并且通过红外和单晶X射线衍射分析对其进行了表征。在配合物1中,镍原子处于手性假八面体[NiN6]的几何构型中,它与三个1,3-丙二胺分子形成了三个六元环。在配合物2中,镍原子除了与两个o-苯二胺分子通过四个Ni-N键形成两个五元环外,它还与两个Cl原子配位形成了反式Ni-Cl2,这不同于以往报道过的镍的二胺配合物。这两个镍的配合物被MAO, MMAO或Et2AlCl活化后,对乙烯的二聚合或三聚合显示了很好的催化活性[对于配合物2,催化活性达到3.59×106 g mol-1 (Ni) h-1]。 相似文献
3.
The synthesis, characterization and methyl methacrylate polymerization behaviors of 2‐(N‐arylimino)pyrrolide nickel complexes are described. The nickel complex [NN]2Ni ( 1 , [NN] = [2‐C(H)NAr‐5‐tBu‐C4H2N]?, Ar = 2,6‐iPr2C6H3) was prepared in good yield by the reaction of [NN]Li with trans‐[Ni(Cl)(Ph)(PPh3)2] in THF. Reaction of [NN]Li with NiBr2(DME) yielded the nickel bromide [NN]Ni(Br)[NNH] ( 2 ). Complexes 1 and 2 were characterized by 1H NMR and IR spectroscopy and elemental analysis, and by X‐ray single crystal analysis. Both complexes, upon activation with methylaluminoxane, are highly active for the polymerization of methyl methacrylate to give high molecular weight polymethylmethacrylate with narrow molecular distributions. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
4.
Four NHC [CNN] pincer nickel (II) complexes, [iPrCNN (CH2)4‐Ni‐Br] ( 5a ), [nBuCNN (CH2)4‐Ni‐Br] ( 5b ), [iPrCNN (Me)2‐Ni‐Br] ( 6a ) and [nBuCNN (Me)2‐Ni‐Br] ( 6b ), bearing unsymmetrical [C (carbene)N (amino)N (amine)] ligands were synthesized by the reactions of [CNN] pincer ligand precursors 4 with Ni (DME)Cl2 in the presence of Et3N. Complexes 5a and 5b are new and were completely characterized. The transfer hydrogenation of ketones catalyzed by the four pincer nickel complexes were explored. Complexes 5a and 6a have better catalytic activity than 5b and 6b . With a combination of NaOtBu/iPrOH/80 °C and 2% catalyst loading of 5a , 77–98% yields of aromatic alcohols could be obtained. 相似文献
5.
Henrike Gehring Ramona Metzinger Christian Herwig Julia Intemann Prof. Dr. Sjoerd Harder Prof. Dr. Christian Limberg 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(5):1629-1636
After the lithiation of PYR‐H2 (PYR2?=[{NC(Me)C(H)C(Me)NC6H3(iPr)2}2(C5H3N)]2?), which is the precursor of an expanded β‐diketiminato ligand system with two binding pockets, its reaction with [NiBr2(dme)] led to a dinuclear nickel(II)–bromide complex, [(PYR)Ni(μ‐Br)NiBr] ( 1 ). The bridging bromide ligand could be selectively exchanged for a thiolate ligand to yield [(PYR)Ni(μ‐SEt)NiBr] ( 3 ). In an attempt to introduce hydride ligands, both compounds were treated with KHBEt3. This treatment afforded [(PYR)Ni(μ‐H)Ni] ( 2 ), which is a mixed valent NiI? μ‐H? NiII complex, and [(PYR‐H)Ni(μ‐SEt)Ni] ( 4 ), in which two tricoordinated NiI moieties are strongly antiferromagnetically coupled. Compound 4 is the product of an initial salt metathesis, followed by an intramolecular redox process that separates the original hydride ligand into two electrons, which reduce the metal centres, and a proton, which is trapped by one of the binding pockets, thereby converting it into an olefin ligand on one of the NiI centres. The addition of a mild acid to complex 4 leads to the elimination of H2 and the formation of a NiIINiII compound, [(PYR)Ni(μ‐SEt)NiOTf] ( 5 ), so that the original NiII(μ‐SEt)NiIIX core of compound 3 is restored. All of these compounds were fully characterized, including by X‐ray diffraction, and their molecular structures, as well as their formation processes, are discussed. 相似文献
6.
Guanghui Sun Lirong Zhang Guanlin Zhang Yuehui Fan Yuhong Wang Guanzhong Lu 《中国化学会会志》2013,60(11):1365-1370
The hydrodechlorination performance of nickel complex catalysts, Ni[phen]2(PF6)2 and Ni[bpy]3(PF6)2, were investigated with [Bmim]Br as the ionic liquid solvent. It is proved that Ni[phen]2(PF6)2 is efficient for the hydrodechlorination of aryl chlorides under mild conditions with water as the hydrogen source. The hydrogen source of reaction is from the water which was confirmed by the deuterium incorporation experiments. Recycling experiments showed a decreasing activity of this catalyst due to a small leaching of nickel complex from the ionic liquid phase during the recycling process where n‐heptane was used as the extractant. A plausible reaction route has been suggested. 相似文献
7.
Ariel G. De Candia Matias Molnar Leonardo D. Slep Ricardo Baggio 《Acta Crystallographica. Section C, Structural Chemistry》2012,68(5):m121-m126
Although it has not proved possible to crystallize the newly prepared cyclam–methylimidazole ligand 1‐[(1‐methyl‐1H‐imidazol‐2‐yl)methyl]‐1,4,8,11‐tetraazacyclotetradecane (LIm1), the trans and cis isomers of an NiII complex, namely trans‐aqua{1‐[(1‐methyl‐1H‐imidazol‐2‐yl)methyl]‐1,4,8,11‐tetraazacyclotetradecane}nickel(II) bis(perchlorate) monohydrate, [Ni(C15H30N6)(H2O)](ClO4)2·H2O, (1), and cis‐aqua{1‐[(1‐methyl‐1H‐imidazol‐2‐yl)methyl]‐1,4,8,11‐tetraazacyclotetradecane}nickel(II) bis(perchlorate), [Ni(C15H30N6)(H2O)](ClO4)2, (2), have been prepared and structurally characterized. At different stages of the crystallization and thermal treatment from which (1) and (2) were obtained, a further two compounds were isolated in crystalline form and their structures also analysed, namely trans‐{1‐[(1‐methyl‐1H‐imidazol‐2‐yl)methyl]‐1,4,8,11‐tetraazacyclotetradecane}(perchlorato)nickel(II) perchlorate, [Ni(ClO4)(C15H30N6)]ClO4, (3), and cis‐{1,8‐bis[(1‐methyl‐1H‐imidazol‐2‐yl)methyl]‐1,4,8,11‐tetraazacyclotetradecane}nickel(II) bis(perchlorate) 0.24‐hydrate, [Ni(C20H36N6)](ClO4)2·0.24H2O, (4); the 1,8‐bis[(1‐methyl‐1H‐imidazol‐2‐yl)methyl]‐1,4,8,11‐tetraazacyclotetradecane ligand is a minor side product, probably formed in trace amounts in the synthesis of LIm1. The configurations of the cyclam macrocycles in the complexes have been analysed and the structures are compared with analogues from the literature. 相似文献
8.
Electrocatalytic Hydrogen Production by a Nickel(II) Complex with a Phosphinopyridyl Ligand
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Ryo Tatematsu Prof. Tomohiko Inomata Prof. Tomohiro Ozawa Prof. Hideki Masuda 《Angewandte Chemie (International ed. in English)》2016,55(17):5247-5250
A novel nickel(II) complex [Ni(L)2Cl]Cl with a bidentate phosphinopyridyl ligand 6‐((diphenylphosphino)methyl)pyridin‐2‐amine (L) was synthesized as a metal‐complex catalyst for hydrogen production from protons. The ligand can stabilize a low Ni oxidation state and has an amine base as a proton transfer site. The X‐ray structure analysis revealed a distorted square‐pyramidal NiII complex with two bidentate L ligands in a trans arrangement in the equatorial plane and a chloride anion at the apex. Electrochemical measurements with the NiII complex in MeCN indicate a higher rate of hydrogen production under weak acid conditions using acetic acid as the proton source. The catalytic current increases with the stepwise addition of protons, and the turnover frequency is 8400 s?1 in 0.1 m [NBu4][ClO4]/MeCN in the presence of acetic acid (290 equiv) at an overpotential of circa 590 mV. 相似文献
9.
Synthesis and Structural Characterization of a Novel Heterodinuclear Vanadium(IV)‐Nickel(II) Complex
A novel VIV‐NiII heterodinuclear complex [VO(cat)2][Ni(1, 2‐PDA)2H2O] ( 1 ) (cat = catechol; 1, 2‐PDA = 1, 2‐propane diamine) was synthesized at low temperature (10 °C) and characterized by IR spectroscopy and X‐ray diffraction. A novel Ni–O=V structure exists in the complex, the vanadyl–catechol moiety and the nickel–diamine moiety are connected by an oxygen bridge; all molecules are further assembled into crystallites by O–H ··· O hydrogen bonds. 相似文献
10.
Dr. Alberto Pérez-Bitrián Kurt F. Hoffmann Konstantin B. Krause Dr. Günther Thiele Prof. Dr. Christian Limberg Prof. Dr. Sebastian Riedel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(63):e202202016
The pentafluoroorthotellurate group (teflate, OTeF5) is able to form species, for which only the fluoride analogues are known. Despite nickel fluorides being widely investigated, nickel teflates have remained elusive for decades. By reaction of [NiCl4]2− and neat ClOTeF5, we have synthesized the homoleptic [Ni(OTeF5)4]2− anion, which presents a distorted tetrahedral structure, unlike the polymeric [NiF4]2−. This high-spin complex has allowed the study of the electronic properties of the teflate group, which can be classified as a weak/medium-field ligand, and therefore behaves as the fluoride analogue also in ligand-field terms. The teflate ligands in [NEt4]2[Ni(OTeF5)4] are easily substituted, as shown by the formation of [Ni(NCMe)6][OTeF5]2 by dissolving it in acetonitrile. Nevertheless, careful reactions with other conventional ligands have enabled the crystallization of nickel teflate complexes with different coordination geometries, i.e. [NEt4]2[trans-Ni(OEt2)2(OTeF5)4] or [NEt4][Ni(bpyMe2)(OTeF5)3]. 相似文献
11.
Xiaoyu Ren Dr. Christophe Gourlaouen Dr. Marcel Wesolek Dr. Pierre Braunstein 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(41):12731-12734
The imidazolium chloride [C3H3N(C3H6NMe2)N{C(Me)(=NDipp)}]Cl ( 1 ; Dipp=2,6‐diisopropyl phenyl), a potential precursor to a tritopic NimineCNHCNamine pincer‐type ligand, reacted with [Ni(cod)2] to give the NiI‐NiI complex 2 , which contains a rare cod‐derived η3‐allyl‐type bridging ligand. The implied intermediate formation of a nickel hydride through oxidative addition of the imidazolium C−H bond did not occur with the symmetrical imidazolium chloride [C3H3N2{C(Me)(=NDipp)}2]Cl ( 3 ). Instead, a Ni−C(sp3) bond was formed, leading to the neutral NimineCHNimine pincer‐type complex Ni[C3H3N2{C(Me)(=NDipp)}2]Cl ( 4 ). Theoretical studies showed that this highly unusual feature in nickel NHC chemistry is due to steric constraints induced by the N substituents, which prevent Ni−H bond formation. Remarkably, ethylene inserted into the C(sp3)−H bond of 4 without nickel hydride formation, thus suggesting new pathways for the alkylation of non‐activated C−H bonds. 相似文献
12.
Seyed Abolfazl Hosseini‐Yazdi Ali Akbar Khandar Hashem Azizi Amir Reza Aref 《无机化学与普通化学杂志》2008,634(11):1943-1949
The 18‐membered mixed‐donor macrocycle 6,7,8,9,10,11,12,13,20,21‐decahydro‐5H, 19H‐dibenzo[b,m][1,15,5,8,11]dioxatriazacyclooctadecin‐20‐ol ( L ), which contains N3O3 donor set, was synthesized. Also two nickel(II) complexes of L have been synthesized and characterized by X‐ray crystallography, FT‐IR, UV‐Vis absorption spectroscopy and elemental analysis. The structure of complexes shows an unexpected anion dependence. Reaction of Ni(ClO4)2·6H2O with L afforded [Ni L ](ClO4)2·CH2Cl2 complex in which L uses all donor atoms and acts as a hexadentate ligand so forming a mononuclear nickel(II) complex in distorted octahedral geometry. Contrasting with this, when NiCl2·6H20 is used, the product complex [{Ni L Cl}2(μ‐Cl)2] is dimeric and consists of two Ni L Cl units bridged by two chloride ions. The coordination geometry of each nickel atom is a distorted octahedral. In this complex L is exo‐coordinated via only three nitrogen atoms to a nickel ion, which is bound to two cis bridging chloride and one non‐bridging chloride too. Also complexing properties of L towards Ni(ClO4)2·6H2O and NiCl2·6H20 have been determined by UV‐Vis titration in methanol. The computer treatment of the data confirmed the 1:1 metal to ligand stoichiometry for two complexes in solution and gave reliable values for corresponding stability constants (logK = 3.00 ± 0.02 with Ni(ClO4)2·6H2O and logK = 3.29 ± 0.06 with NiCl2·6H20). 相似文献
13.
Gabriele Hierlmeier Peter Coburger Nicolaas P. van Leest Bas de Bruin Robert Wolf 《Angewandte Chemie (International ed. in English)》2020,59(33):14148-14153
The reaction of zerovalent nickel compounds with white phosphorus (P4) is a barely explored route to binary nickel phosphide clusters. Here, we show that coordinatively and electronically unsaturated N‐heterocyclic carbene (NHC) nickel(0) complexes afford unusual cluster compounds with P1, P3, P5 and P8 units. Using [Ni(IMes)2] [IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazolin‐2‐ylidene], electron‐deficient Ni3P4 and Ni3P6 clusters have been isolated, which can be described as superhypercloso and hypercloso clusters according to the Wade–Mingos rules. Use of the bulkier NHC complexes [Ni(IPr)2] or [(IPr)Ni(η6‐toluene)] [IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene] affords a closo‐Ni3P8 cluster. Inverse‐sandwich complexes [(NHC)2Ni2P5] (NHC=IMes, IPr) with an aromatic cyclo‐P5? ligand were identified as additional products. 相似文献
14.
《中国化学会会志》2017,64(2):205-216
In the present work, the nickel(II ) synergist complex with isobutyric acid (HLI ) and 5‐hydroxy‐4‐octanone oxime (HBI ), which were the corresponding short‐chain analogs of the active synergistic mixture of Versatic10 (HL ) and Lix63 (5,8‐diethyl‐7‐hydroxy‐6‐dodecanoneoxime, HB ), was prepared and studied by single‐crystal X‐ray diffraction (XRD ). The crystal structure of the nickel(II ) synergist complex showed that the composition of the complex was Ni(LI )2(HBI )2 with a cis ‐form octahedron geometry structure. Both intra‐ and intermolecular hydrogen bonding were observed in the crystal lattice. Compared with the free ligands, similar band shifts of Fourier transform infrared (FT‐IR ) spectra assigned to the stretching vibration of carbon–oxygen single bond (C O), the stretching vibration of carbon–nitrogen double bond (CN), and the disappearance of the scissoring vibration of α‐hydroxy (OH ) were correspondingly found in both the nickel(II ) synergist complex and the extracted nickel(II ) complex in the nonpolar organic phase. Combined with the results from ESI‐MS , XRD , and slope analysis, it was concluded that the major species of the extracted nickel(II ) complex in the nonpolar organic phase might possess a similar coordination structure [Ni(HB )2(L)2] as the nickel(II ) synergist complex, along with the neutral complex [Ni(HB )(B)2]. 相似文献
15.
Dr. Qingsong Dong Prof. Xiao‐Juan Yang Shida Gong Dr. Qiong Luo Prof. Qian‐Shu Li Prof. Ji‐Hu Su Dr. Yanxia Zhao Prof. Biao Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(45):15240-15247
A nickel? nickel‐bonded complex, [{Ni(μ‐L.?)}2] ( 1 ; L=[(2,6‐iPr2C6H3)NC(Me)]2), was synthesized from reduction of the LNiBr2 precursor by sodium metal. Further controllable reduction of 1 with 1.0, 2.0 and 3.0 equiv of Na, respectively, afforded the singly, doubly, and triply reduced compounds [Na(DME)3] ? [{Ni(μ‐L.?)}2] ( 2 ; DME=1,2‐dimethoxyethane), [Na(Et2O)]Na[(L.?)Ni? NiL2?] ( 3 ), and [Na(Et2O)]2Na[L2?Ni? NiL2?] ( 4 ). Here L represents the neutral ligand, L.? denotes its radical monoanion, and L2? is the dianion. All of the four compounds feature a short Ni? Ni bond from 2.2957(6) to 2.4649(8) Å. Interestingly, they display two different structures: the perpendicular ( 1 and 2 ) and the coaxial ( 3 and 4 ) structure, in which the metal? metal bond axis is perpendicular to or collinear with the axes of the α‐diimine ligands, respectively. The electronic structures, Ni? Ni bonding nature, and energetic comparisons of the two structure types were investigated by DFT computations. 相似文献
16.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(44):13950-13954
Three oxidation states (+2, +3, +4) of an octahedral nickel center were stabilized in a newly prepared RhNiRh trinuclear complex, [Ni{Rh(apt)3}2]n + (apt=3‐ aminopropanethiolate), in which the nickel center was bound by six thiolato donors sourced from two redox‐inert fac ‐[RhIII(apt)3] octahedral units. The three oxidation states of the octahedral nickel center were fully characterized by single‐crystal X‐ray crystallography, as well as spectroscopic, electrochemical, and magnetic measurements; all three were interconvertible, and the conversion was accompanied by changes in color, magnetism, and Jahn–Teller distortion. 相似文献
17.
Importance of a Fluorine Substituent for the Preparation of meta‐ and para‐Pentafluoro‐λ6‐sulfanyl‐Substituted Pyridines
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Dr. Mikhail Kosobokov Benqiang Cui Dr. Andrii Balia Kohei Matsuzaki Etsuko Tokunaga Norimichi Saito Prof. Dr. Norio Shibata 《Angewandte Chemie (International ed. in English)》2016,55(36):10781-10785
Although there are ways to synthesize ortho‐pentafluoro‐λ6‐sulfanyl (SF5) pyridines, meta‐ and para‐SF5‐substituted pyridines are rare. We disclose herein a general route for their synthesis. The fundamental synthetic approach is the same as reported methods for ortho‐SF5‐substituted pyridines and SF5‐substituted arenes, that is, oxidative chlorotetrafluorination of the corresponding disulfides to give pyridylsulfur chlorotetrafluorides (SF4Cl‐pyridines), followed by chloride/fluoride exchange with fluorides. However, the trick in this case is the presence on the pyridine ring of at least one fluorine atom, which is essential for the successful transformation of the disulfides into m‐and p‐SF5‐pyridines. After enabling the synthesis of an SF5‐substituted pyridine, ortho‐F groups can be efficiently substituted by C, N, S, and O nucleophiles through an SNAr pathway. This methodology provides access to a variety of previously unavailable SF5‐substituted pyridine building blocks. 相似文献
18.
1,1‐(Bicyclononyl‐9‐phosphino)hendecanoic acid and potassium 1,1‐(biscyclohexylphosphino)hendecylate were synthesized. A model nickel complex [η3−C8H13]Ni[(C8H14)P(CH2)10COO] containing a 14‐membered chelate ring was also synthesized. The catalytic activity of this large chelate ring nickel complex for the oligomerization of ethylene was studied and compared with that of six‐membered ring chelate nickel complexes. The influence of the chelate ring was rationalized in terms of intramolecular rotation. The 14‐membered ring P/O chelate nickel complex was shown to have efficient catalytic activity for the oligomerization of ethylene to α‐olefins. Copyright © 2000 John Wiley & Sons, Ltd. 相似文献
19.
Jan Ellermeier Ralph Sthler Wolfgang Bensch 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(2):m70-m73
Both title compounds, bis[tris(2‐aminoethyl)amine]nickel(II) dichloride, [Ni(tren)2]Cl2, (I), and bis[tris(2‐aminoethyl)amine]nickel(II) tetrathiotungstate, [Ni(tren)2]WS4, (II), contain the [Ni(tren)2]2+ cation [tren is tris(2‐aminoethyl)amine, C6H18N4]. The tren molecule acts as a tridentate ligand around the central Ni atom, with the remaining primary amine group not bound to the central atom. In (I), Ni2+ is located on a centre of inversion surrounded by one crystallographically independent tren molecule. In the [Ni(tren)2]2+ cation of (II), the Ni atom is bound to two crystallographically independent tren molecules. The Ni atoms in the [Ni(tren)2]2+ complexes are in a distorted octahedral environment consisting of six N atoms from the chelating tren molecules. The counter‐ions are chloride anions in (I) and the tetrahedral [WS4]2? anion in (II). Hydrogen bonding is observed in both compounds. 相似文献
20.
Vasudevan Subramaniyan Ashok Kumar Anbarasu Govindaraj Ganesan Mani 《Acta Crystallographica. Section C, Structural Chemistry》2019,75(6):734-739
The reaction of NiCl2 with 1,3‐bis[(diphenylphosphanyl)methyl]hexahydropyrimidine in the presence of 2,6‐dimethylphenyl isocyanide and KPF6 afforded a new pentacoordinated PCP pincer NiII complex, namely {1,3‐bis[(diphenylphosphanyl)methyl]hexahydropyrimidin‐2‐yl‐κN2}(2,6‐dimethylphenyl isocyanide‐κC)nickel(II) hexafluoridophosphate 0.70‐hydrate, [Ni(C9H9N)(C30H30ClN2P2)]PF6·0.7H2O or [NiCl{C(NCH2PPh2)2(CH2)3‐κ3P,C,P′}(Xylyl‐NC)]PF6·0.7H2O, in very good yield. Its X‐ray structure showed a distorted square‐pyramidal geometry and the compound does not undergo dissociation in solution, as shown by variable‐temperature NMR and UV–Vis studies. Density functional theory (DFT) calculations provided an insight into the bonding; the nickel dsp2‐hybridized orbitals form the basal plane and the nearly pure p orbital forms the axial bond. This is consistent with the NBO (natural bond orbital) analysis of analogous nickel(II) complexes. 相似文献