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1.
《Acta Crystallographica. Section C, Structural Chemistry》2018,74(5):590-598
Crystals of mononuclear tris[bis(2,6‐diisopropylphenyl) phosphato‐κO]pentakis(methanol‐κO)lanthanide methanol monosolvates of lanthanum, [La(C24H34O4P)3(CH3OH)5]·CH3OH, ( 1 ), cerium, [Ce(C24H34O4P)3(CH3OH)5]·CH3OH, ( 2 ), and neodymium, [Nd(C24H34O4P)3(CH3OH)5]·CH3OH, ( 3 ), have been obtained by reactions between LnCl3(H2O)n (n = 6 or 7) and lithium bis(2,6‐diisopropylphenyl) phosphate in a 1:3 molar ratio in methanol media. Compounds ( 1 )–( 3 ) crystallize in the monoclinic P21/c space group and have isomorphous crystal structures. All three bis(2,6‐diisopropylphenyl) phosphate ligands display a κO‐monodentate coordination mode. The coordination number of the metal atom is 8. Each [Ln{O2P(O‐2,6‐iPr2C6H3)2}3(CH3OH)5] molecular unit exhibits four intramolecular O—H…O hydrogen bonds, forming six‐membered rings. The unit forms two intermolecular O—H…O hydrogen bonds with one noncoordinating methanol molecule. All six hydroxy H atoms are involved in hydrogen bonding within the [Ln{O2P(O‐2,6‐iPr2C6H3)2}3(CH3OH)5]·CH3OH unit. This, along with the high steric hindrance induced by the three bulky diaryl phosphate ligands, prevents the formation of a hydrogen‐bond network. Complexes ( 1 )–( 3 ) exhibit disorder of two of the isopropyl groups of the phosphate ligands. The cerium compound ( 2 ) demonstrates an essential catalytic inhibition in the thermal decomposition of polydimethylsiloxane in air at 573 K. Catalytic systems based on the neodymium complex tris[bis(2,6‐diisopropylphenyl) phosphato‐κO]neodymium, ( 3′ ), which was obtained as a dry powder of ( 3 ) upon removal of methanol, display a high catalytic activity in isoprene and butadiene polymerization. 相似文献
2.
《Acta Crystallographica. Section C, Structural Chemistry》2017,73(10):820-827
The crystal structures of rare‐earth diaryl‐ or dialkylphosphate derivatives are poorly explored. Crystals of bis[bis(2,6‐diisopropylphenyl)phosphato‐κO ]chloridotetrakis(methanol‐κO )neodymium methanol disolvate, [Nd(C24H34O4P)Cl(CH4O)4]·2CH3OH, (1), and of the lutetium, [Lu(C24H34O4P)Cl(CH4O)4]·2CH3OH, (2), and yttrium, [Y(C24H34O4P)Cl(CH4O)4]·2CH3OH, (3), analogues have been obtained by reactions between lithium bis(2,6‐diisopropylphenyl)phosphate and LnCl3(H2O)6 (in a 2:1 ratio) in methanol. Compounds (1)–(3) crystallize in the C 2/c space group. Their crystal structures are isomorphous. The molecule possesses C 2 symmetry with a twofold crystallographic axis passing through the Ln and Cl atoms. The bis(2,6‐diisopropylphenyl)phosphate ligands all display a κ1O‐monodentate coordination mode. The coordination polyhedron for the metal atom [coordination number (CN) = 7] is a distorted pentagonal bipyramid. Each [Ln{O2P(O‐2,6‐iPr2C6H3)2}2Cl(CH3OH)4] molecular unit exhibits two intramolecular O—H…O hydrogen bonds, forming six‐membered rings, and two intramolecular O—H…Cl interactions, forming four‐membered rings. Intermolecular O—H…O hydrogen bonds connect each unit via four noncoordinating methanol molecules with four other units, forming a two‐dimensional hydrogen‐bond network. Crystals of bis[bis(2,6‐diisopropylphenyl)phosphato‐κO ]tetrakis(methanol‐κO )(nitrato‐κ2O ,O ′)neodymium methanol disolvate, [Nd(C24H34O4P)(NO3)(CH4O)4]·2CH3OH, (4), have been obtained in an analogous manner from NdCl3(H2O)6. Compound (4) also crystalizes in the C 2/c space group. Its crystal structure is similar to those of (1)–(3). The κ2O ,O ′‐bidentate nitrate anion is disordered over a twofold axis, being located nearly on it. Half of the molecule is crystallographically unique (CNNd = 8). Unlike (1)–(3), complex (4) exhibits disorder of all three methanol molecules, one isopropyl group of the phosphate ligand and the NO3− ligand. The structure of (4) displays intra‐ and intermolecular O—H…O hydrogen bonds similar to those in (1)–(3). Compounds (1)–(4) represent the first reported mononuclear bis[bis(diaryl/dialkyl)phosphate] rare‐earth complexes. 相似文献
3.
Padavattan Govindaswamy Julien Furrer Georg Süss‐Fink Bruno Therrien 《无机化学与普通化学杂志》2008,634(8):1349-1352
A large cationic triangular metallo‐prism, [Ru6(p‐PriC6H4Me)6(tpt)2(dhbq)3]6+ ( 1 )6+, incorporating p‐cymene ruthenium building blocks, bridged by 2,5‐dihydroxy‐1,4‐benzoquinonato (dhbq) ligands, and connected by two 2,4,6‐tri(pyridin‐4‐yl)‐1,3,5‐triazine (tpt) subunits, allows the permanent encapsulation of the triphenylene derivatives hexahydroxytriphenylene, C18H6(OH)6 and hexamethoxytriphenylene, C18H6(OMe)6. These two cationic carceplex systems [C18H6(OH)6⊂ 1 ]6+ and [C18H6(OMe)6⊂ 1 ]6+ have been isolated as their triflate salts. The molecular structure of these systems has been established by one‐dimensional 1H ROESY NMR experiments as well as by the single‐crystal structure analysis of [C18H6(OMe)6⊂ 1 ][O3SCF3]6. 相似文献
4.
Alexander N. Tavtorkin Sof'ya A. Korchagina Pavel D. Komarov Alexey A. Vinogradov Andrei V. Churakov Ilya E. Nifant'ev Mikhail E. Minyaev 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(1):93-103
The crystal structures of three unusual chromium organophosphate complexes have been determined, namely, bis(μ‐butyl 2,6‐di‐tert‐butyl‐4‐methylphenyl hydrogen phosphato‐κO:κO′)di‐μ‐hydroxido‐bis[(butyl 2,6‐di‐tert‐butyl‐4‐methylphenyl hydrogen phosphato‐κO)(butyl 2,6‐di‐tert‐butyl‐4‐methylphenyl phosphato‐κO)chromium](Cr—Cr) heptane disolvate or {Cr2(μ2‐OH)2[μ2‐PO2(OBu)(O‐2,6‐tBu2‐4‐MeC6H2)‐κO:κO′]2[PO2(OBu)(O‐2,6‐tBu2‐4‐MeC6H2)‐κO]2[HOPO(OBu)(O‐2,6‐tBu2‐4‐MeC6H2)‐κO]2}·2C7H16, [Cr2(C19H32O4P)4(C19H33O4P)2(OH)2]·2C7H16, denoted ( 1 )·2(heptane), [μ‐bis(2,6‐diisopropylphenyl) phosphato‐1κO:2κO′]bis[bis(2,6‐diisopropylphenyl) phosphato]‐1κO,2κO‐chlorido‐2κCl‐triethanol‐1κ2O,2κO‐di‐μ‐ethanolato‐1κ2O:2κ2O‐dichromium(Cr—Cr) ethanol monosolvate or {Cr2(μ2‐OEt)2[μ2‐PO2(O‐2,6‐iPr2‐C6H3)2‐κO:κO′][PO2(O‐2,6‐iPr2‐C6H3)2‐κO]2Cl(EtOH)3}·EtOH, [Cr2(C2H5O)2(C24H34O4P)3Cl(C2H6O)3]·C2H6O, denoted ( 2 )·EtOH, and di‐μ‐ethanolato‐1κ2O:2κ2O‐bis{[bis(2,6‐diisopropylphenyl) hydrogen phosphato‐κO][bis(2,6‐diisopropylphenyl) phosphato‐κO]chlorido(ethanol‐κO)chromium}(Cr—Cr) benzene disolvate or {Cr2(μ2‐OEt)2[PO2(O‐2,6‐iPr2‐C6H3)2‐κO]2[HOPO(O‐2,6‐iPr2‐C6H3)2‐κO]2Cl2(EtOH)2}·2C6H6, [Cr2(C2H5O)2(C24H34O4P)2(C24H35O4P)2Cl2(C2H6O)2]·2C6H6, denoted ( 3 )·2C6H6. Complexes ( 1 )–( 3 ) have been synthesized by an exchange reaction between the in‐situ‐generated corresponding lithium or potassium disubstituted phosphates with CrCl3(H2O)6 in ethanol. The subsequent crystallization of ( 1 ) from heptane, ( 2 ) from ethanol and ( 3 ) from an ethanol/benzene mixture allowed us to obtain crystals of ( 1 )·2(heptane), ( 2 )·EtOH and ( 3 )·2C6H6, whose structures have the monoclinic P21, orthorhombic P212121 and triclinic P space groups, respectively. All three complexes have binuclear cores with a single Cr—Cr bond, i.e. Cr2O6P2 in ( 1 ), Cr2PO4 in ( 2 ) and Cr2O2 in ( 3 ), where the Cr atoms are in distorted octahedral environments, formally having 16 ē per Cr atom. The complexes have bridging ligands μ2‐OH in ( 1 ) or μ2‐OEt in ( 2 ) and ( 3 ). The organophosphate ligands demonstrate terminal κO coordination modes in ( 1 )–( 3 ) and bridging μ2‐κO:κO′ coordination modes in ( 1 ) and ( 2 ). All the complexes exhibit hydrogen bonding: two intramolecular Ophos…H—Ophos interactions in ( 1 ) and ( 3 ) form two {H[PO2(OR)2]2} associates; two intramolecular Cl…H—OEt hydrogen bonds additionally stabilize the Cr2O2 core in ( 3 ); two intramolecular Ophos…H—OEt interactions and two O…H—O intermolecular hydrogen bonds with a noncoordinating ethanol molecule are observed in ( 2 )·EtOH. The presence of both basic ligands (OH? or OEt?) and acidic [H(phosphate)2]? associates at the same metal centres in ( 1 ) and ( 3 ) is rather unusual. Complexes may serve as precatalysts for ethylene polymerization under mild conditions, providing polyethylene with a small amount of short‐chain branching. The formation of a small amount of α‐olefins has been detected in this reaction. 相似文献
5.
Alexander J. Blake Naomi A. Harris Deborah L. Kays William Lewis Graeme J. Moxey 《Acta Crystallographica. Section C, Structural Chemistry》2010,66(8):m204-m206
The solid‐state structure of the title compound, [Na2Mn2(C32H56N2OSi2)2O2] or [1,8‐C10H6(NSiiPr3)2Mn(μ3‐O)Na(THF)]2, which lies across a crystallographic twofold axis, exhibits a central [Mn2O2Na2]4+ core, with two oxide groups, each triply bridging between the two MnIII ions and an Na+ ion. Additional coordination is provided to each MnIII centre by a 1,8‐C10H6(NSiiPr3)2 [1,8‐bis(triisopropylsilylamido)naphthalene] ligand and to the Na+ centres by a tetrahydrofuran molecule. The presence of an additional Na...H—C agostic interaction potentially contributes to the distortion around the bridging oxide group. 相似文献
6.
Cristiano Zuccaccia Gianfranco Bellachioma Giuseppe Cardaci Alceo Macchioni Barbara Binotti Carla Carfagna 《Helvetica chimica acta》2006,89(8):1524-1546
Palladacyclic compounds [Pd(C6H4(C6H5C?O)C?N? R)(N? N)] [X] (R = Et, iPr, 2,6‐iPr2C6H3; N? N = bpy = 2,2′‐bipyridine, or 1,4‐(o,o′‐dialkylaryl)‐1,4‐diazabuta‐1,3‐dienes; [X]? = [BF4]? or [PF6]?) were synthesized from the dimers [{Pd(C6H4(C6H5C?O)C?N? R)(μ‐Cl)}2] and N? N ligands. Their interionic structure in CD2Cl2 was determined by means of 19F,1H‐HOESY experiments and compared with that in the solid state derived from X‐ray single‐crystal studies. [Pd(C6H4(C6H5C?O)C?N? R)(N? N)] [X] complexes were found to copolymerize CO and p‐methylstyrene affording syndiotactic or isotactic copolymers when bpy or 1,4‐(o,o′‐dimethylaryl)‐1,4‐diazabuta‐1,3‐dienes were used, respectively. The reactions with CO and p‐methylstyrene of the bpy derivatives were investigated. Two intermediates derived from a single and a double insertion of CO into the Pd? C bonds were isolated and completely characterized in solution. 相似文献
7.
Wannida Apisuk Alexandra G. Trambitas Boonyarach Kitiyanan Matthias Tamm Kotohiro Nomura 《Journal of polymer science. Part A, Polymer chemistry》2013,51(12):2575-2580
Ethylene copolymerizations with norbornene (NBE) using half‐titanocenes containing imidazolin‐2‐iminato ligands, Cp′TiCl2[1,3‐R2(CHN)2C?N] [Cp′ = Cp ( 1 ), tBuC5H4 ( 2 ); R = tBu ( a ), 2,6‐iPr2C6H3 ( b )], have been explored in the presence of methylaluminoxane (MAO) cocatalyst. Complex 1a exhibited remarkable catalytic activity with better NBE incorporation, affording high‐molecular‐weight copolymers with uniform molecular weight distributions, whereas the tert‐BuC5H4 analog ( 2a ) showed low activity, and the resultant polymer prepared by the Cp‐2,6‐diisopropylphenyl analog ( 1b ) possessed broad molecular weight distribution. The microstructure analysis of the poly(ethylene‐co‐NBE)s prepared by 1a suggests the formation of random copolymers including two and three NBE repeating units. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2575–2580 相似文献
8.
Bis(β‐diketiminato) lanthanide amides: synthesis,structure and catalysis for the polymerization of l‐lactide and ε‐caprolactone 下载免费PDF全文
Yu Zheng Rui Jiao Xiao‐dong Shen Ming‐qiang Xue Ying‐ming Yao Yong Zhang Qi Shen 《应用有机金属化学》2014,28(6):461-470
Treatment of the chlorides (L2,6‐iPr2Ph)2LnCl (L2,6‐iPr2Ph = [(2,6‐iPr2C6H3)NC(Me)CHC(Me)N(C6H5)]?) with 1 equiv. of NaNH(2,6‐iPr2C6H3) afforded the monoamides (L2,6‐iPr2Ph)2LnNH(2,6‐iPr2C6H3) (Ln = Y ( 1 ), Yb ( 2 )) in good yields. Anhydrous LnCl3 reacted with 2 equiv. of NaL2,6‐iPr2Ph in THF, followed by treatment with 1 equiv. of NaNH(2,6‐iPr2C6H3), giving the analogues (L2,6‐iPr2Ph)2LnNH(2,6‐iPr2C6H3) (Ln = Sm ( 3 ), Nd ( 4 )). Two monoamido complexes stabilized by two L2‐Me ligands, (L2‐Me)2LnNH(2,6‐iPr2C6H3) (L2‐Me = [N(2‐MeC6H4)C(Me)]2CH)?; Ln = Y ( 5 ), Yb ( 6 )), were also synthesized by the latter route. Complexes 1 , 2 , 3 , 4 , 5 , 6 were fully characterized, including X‐ray crystal structure analyses. Complexes 1 , 2 , 3 , 4 , 5 , 6 are isostructural. The central metal in each complex is ligated by two β‐diketiminato ligands and one amido group in a distorted trigonal bipyramid. All the complexes were found to be highly active in the ring‐opening polymerization of L‐lactide (L‐LA) and ε‐caprolactone (ε‐CL) to give polymers with relatively narrow molar mass distributions. The activity depends on both the central metal and the ligand (Yb < Y < Sm ≈ Nd and L2‐Me < L2,6‐iPr2Ph). Remarkably, the binary 3/benzyl alcohol (BnOH) system exhibited a striking ‘immortal’ nature and proved able to quantitatively convert 5000 equiv. of L‐LA with up to 100 equiv. of BnOH per metal initiator. All the resulting PLAs showed monomodal, narrow distributions (Mw/Mn = 1.06 ? 1.08), with molar mass (Mn) decreasing proportionally with an increasing amount of BnOH. The binary 4/BnOH system also exhibited an ‘immortal’ nature in the polymerization of ε‐CL in toluene. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
9.
Guangrong Tang Yue‐Jian Lin Guo‐Xin Jin 《Journal of polymer science. Part A, Polymer chemistry》2008,46(2):489-500
A series of new indanimine ligands [ArN?CC2H3(CH3)C6H2(R)OH] (Ar = Ph, R = Me ( 1 ), R = H ( 2 ), and R = Cl ( 3 ); Ar = 2,6‐i‐Pr2C6H3, R = Me ( 4 ), R = H ( 5 ), and R = Cl ( 6 )) were synthesized and characterized. Reaction of indanimines with Ni(OAc)2·4H2O results in the formation of the trinuclear hexa(indaniminato)tri (nickel(II)) complexes Ni3[ArN = CC2H3(CH3)C6H2(R)O]6 (Ar = Ph, R = Me ( 7 ), R = H ( 8 ), and R = Cl ( 9 )) and the mononuclear bis(indaniminato)nickel (II) complexes Ni[ArN?CC2H3(CH3)C6H2(R)O]2 (Ar = 2,6‐i‐Pr2C6H3, R = Me ( 10 ), R = H ( 11 ), and R = Cl ( 12 )). All nickel complexes were characterized by their IR, NMR spectra, and elemental analyses. In addition, X‐ray structure analyses were performed for complexes 7 , 10 , 11 , and 12 . After being activated with methylaluminoxane (MAO), these nickel(II) complexes can polymerize norbornene to produce addition‐type polynorbornene (PNB) with high molecular weight Mv (106 g mol?1), highly catalytic activities up to 2.18 × 107 gPNB mol?1 Ni h?1. Catalytic activities and the molecular weight of PNB have been investigated for various reaction conditions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 489–500, 2008 相似文献
10.
Vaduganathan Yasodha Subbaiah Govindarajan John N. Low Christopher Glidewell 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(5):m207-m215
The structures of five metal complexes containing the 4‐oxo‐4H‐pyran‐2,6‐dicarboxylate dianion illustrate the remarkable coordinating versatility of this ligand and the great structural diversity of its complexes. In tetraaquaberyllium 4‐oxo‐4H‐pyran‐2,6‐dicarboxylate, [Be(H2O)4](C7H2O6), (I), the ions are linked by eight independent O—H...O hydrogen bonds to form a three‐dimensional hydrogen‐bonded framework structure. Each of the ions in hydrazinium(2+) diaqua(4‐oxo‐4H‐pyran‐2,6‐dicarboxylato)calcate, (N2H6)[Ca(C7H2O6)2(H2O)2], (II), lies on a twofold rotation axis in the space group P2/c; the anions form hydrogen‐bonded sheets which are linked into a three‐dimensional framework by the cations. In bis(μ‐4‐oxo‐4H‐pyran‐2,6‐dicarboxylato)bis[tetraaquamanganese(II)] tetrahydrate, [Mn2(C7H2O6)2(H2O)8]·4H2O, (III), the metal ions and the organic ligands form a cyclic centrosymmetric Mn2(C7H2O6)2 unit, and these units are linked into a complex three‐dimensional framework structure containing 12 independent O—H...O hydrogen bonds. There are two independent CuII ions in tetraaqua(4‐oxo‐4H‐pyran‐2,6‐dicarboxylato)copper(II), [Cu(C7H2O6)(H2O)4], (IV), and both lie on centres of inversion in the space group P; the metal ions and the organic ligands form a one‐dimensional coordination polymer, and the polymer chains are linked into a three‐dimensional framework containing eight independent O—H...O hydrogen bonds. Diaqua(4‐oxo‐4H‐pyran‐2,6‐dicarboxylato)cadmium monohydrate, [Cd(C7H2O6)(H2O)2]·H2O, (V), forms a three‐dimensional coordination polymer in which the organic ligand is coordinated to four different Cd sites, and this polymer is interwoven with a complex three‐dimensional framework built from O—H...O hydrogen bonds. 相似文献
11.
Ya-Qian Zhang Vladislav A. Blatov Xiu-Xiu Lv Ding-Yi Tang Lin-Lu Qian Ke Li Bao-Long Li 《Acta Crystallographica. Section C, Structural Chemistry》2019,75(7):960-968
Coordination polymers (CPs) have been widely studied because of their diverse and adjustable topologies and wide‐ranging applications in luminescence, chemical sensors, magnetism, photocatalysis, gas adsorption and separation. In the present work, two coordination polymers, namely poly[(μ5‐benzene‐1,3,5‐tricarboxylato‐κ6O1:O1′:O3:O3:O5,O5′){μ3‐1,3‐bis[(1,2,4‐triazol‐4‐yl)methyl]benzene‐κ3N:N′:N′′}di‐μ3‐hydroxido‐dicobalt(II)], [Co2(C9H3O6)(OH)(C12H12N6)]n or [Co2(btc)(OH)(mtrb)]n, (1), and poly[[diaquabis(μ3‐benzene‐1,3,5‐tricarboxylato‐κ3O1:O3:O5)bis{μ3‐1,3‐bis[(1,2,4‐triazol‐4‐yl)methyl]benzene‐κ3N:N′:N′′}tetra‐μ3‐hydroxido‐tetracopper(II)] monohydrate], {[Cu4(C9H3O6)2(OH)2(C12H12N6)2(H2O)2]·H2O}n or {[Cu4(btc)2(OH)2(mtrb)2(H2O)2]·H2O}n, (2), were synthesized by the hydrothermal method using 1,3‐bis[(1,2,4‐triazol‐4‐yl)methyl]benzene (mtrb) and benzene‐1,3,5‐tricarboxylate (btc3?). CP (1) exhibits a (3,8)‐coordinated three‐dimensional (3D) network of the 3,8T38 topological type, with a point symbol of {4,5,6}2{42·56·616·72·82}, based on the tetranuclear hydroxide cobalt(II) cluster [Co4(μ3‐OH)2]. CP (2) shows a (3,8)‐coordinated tfz‐d topology, with a point symbol of {43}2{46·618·84}, based on the tetranuclear hydroxide copper(II) cluster [Cu4(μ3‐OH)2]. The different (3,8)‐coordinated 3D networks based on tetranuclear hydroxide–metal clusters of (1) and (2) are controlled by the different central metal ions [CoII for (1) and CuII for (2)]. The thermal stabilities and solid‐state optical diffuse‐reflection spectra were measured. The energy band gaps (Eg) obtained for (1) and (2) were 2.72 and 2.29 eV, respectively. CPs (1) and (2) exhibit good photocatalytic degradation of the organic dyes methylene blue (MB) and rhodamine B (RhB) under visible‐light irradiation. 相似文献
12.
The Ruthenostannylene Complex [Cp*(IXy)H2Ru‐Sn‐Trip]: Providing Access to Unusual Ru‐Sn Bonded Stanna‐imine,Stannene, and Ketenylstannyl Complexes 下载免费PDF全文
Hsueh‐Ju Liu Micah S. Ziegler Prof. Dr. T. Don Tilley 《Angewandte Chemie (International ed. in English)》2015,54(22):6622-6626
Reactivity studies of the thermally stable ruthenostannylene complex [Cp*(IXy)(H)2Ru? Sn? Trip] ( 1 ; IXy=1,3‐bis(2,6‐dimethylphenyl)imidazol‐2‐ylidene; Cp*=η5‐C5Me5; Trip=2,4,6‐iPr3C6H2) with a variety of organic substrates are described. Complex 1 reacts with benzoin and an α,β‐unsaturated ketone to undergo [1+4] cycloaddition reactions and afford [Cp*(IXy)(H)2RuSn(κ2‐O,O‐OCPhCPhO)Trip] ( 2 ) and [Cp*(IXy)(H)2RuSn(κ2‐O,C‐OCPhCHCHPh)Trip] ( 3 ), respectively. The reaction of 1 with ethyl diazoacetate resulted in a tin‐substituted ketene complex [Cp*(IXy)(H)2RuSn(OC2H5)(CHCO)Trip] ( 4 ), which is most likely a decomposition product from the putative ruthenium‐substituted stannene complex. The isolation of a ruthenium‐substituted stannene [Cp*(IXy)(H)2RuSn(?Flu)Trip] ( 5 ) and stanna‐imine [Cp*(IXy)(H)2RuSn(κ2‐N,O‐NSO2C6H4Me)Trip] ( 6 ) complexes was achieved by treatment of 1 with 9‐diazofluorene and tosyl azide, respectively. 相似文献
13.
Hsueh‐Ju Liu Micah S. Ziegler T. Don Tilley 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(22):6722-6726
Reactivity studies of the thermally stable ruthenostannylene complex [Cp*(IXy)(H)2Ru Sn Trip] ( 1 ; IXy=1,3‐bis(2,6‐dimethylphenyl)imidazol‐2‐ylidene; Cp*=η5‐C5Me5; Trip=2,4,6‐iPr3C6H2) with a variety of organic substrates are described. Complex 1 reacts with benzoin and an α,β‐unsaturated ketone to undergo [1+4] cycloaddition reactions and afford [Cp*(IXy)(H)2RuSn(κ2‐O,O‐OCPhCPhO)Trip] ( 2 ) and [Cp*(IXy)(H)2RuSn(κ2‐O,C‐OCPhCHCHPh)Trip] ( 3 ), respectively. The reaction of 1 with ethyl diazoacetate resulted in a tin‐substituted ketene complex [Cp*(IXy)(H)2RuSn(OC2H5)(CHCO)Trip] ( 4 ), which is most likely a decomposition product from the putative ruthenium‐substituted stannene complex. The isolation of a ruthenium‐substituted stannene [Cp*(IXy)(H)2RuSn(Flu)Trip] ( 5 ) and stanna‐imine [Cp*(IXy)(H)2RuSn(κ2‐N,O‐NSO2C6H4Me)Trip] ( 6 ) complexes was achieved by treatment of 1 with 9‐diazofluorene and tosyl azide, respectively. 相似文献
14.
Dr. Shenglai Yao Dr. Yun Xiong Dr. Tibor Szilvási Prof. Dr. Hansjörg Grützmacher Prof. Dr. Matthias Driess 《Angewandte Chemie (International ed. in English)》2016,55(15):4781-4785
The first 4π‐electron resonance‐stabilized 1,3‐digerma‐2,4‐diphosphacyclobutadiene [LH2Ge2P2] 4 (LH=CH[CHNDipp]2 Dipp=2,6‐iPr2C6H3) with four‐coordinate germanium supported by a β‐diketiminate ligand and two‐coordinate phosphorus atoms has been synthesized from the unprecedented phosphaketenyl‐functionalized N‐heterocyclic germylene [LHGe‐P=C=O] 2 a prepared by salt‐metathesis reaction of sodium phosphaethynolate (P≡C?ONa) with the corresponding chlorogermylene [LHGeCl] 1 a . Under UV/Vis light irradiation at ambient temperature, release of CO from the P=C=O group of 2 a leads to the elusive germanium–phosphorus triply bonded species [LHGe≡P] 3 a , which dimerizes spontaneously to yield black crystals of 4 as isolable product in 67 % yield. Notably, release of CO from the bulkier substituted [LtBuGe‐P=C=O] 2 b (LtBu=CH[C(tBu)N‐Dipp]2) furnishes, under concomitant extrusion of the diimine [Dipp‐NC(tBu)]2, the bis‐N,P‐heterocyclic germylene [DippNC(tBu)C(H)PGe]2 5 . 相似文献
15.
Ana María Atria Alan Astete Maria Teresa Garland Ricardo Baggio 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(11):m411-m414
The title isomorphous compounds, tetra‐μ‐but‐2‐enoato‐bis[diaqua(but‐2‐enoato)dysprosium(III)]–2,6‐diaminopurine (1/2), [Dy2(C4H5O2)6(H2O)4]·2C5H6N6, and tetra‐μ‐but‐2‐enoato‐bis[diaqua(but‐2‐enoato)holmium(III)]–2,6‐diaminopurine (1/2), [Ho2(C4H5O2)6(H2O)4]·2C5H6N6, consist of [Ln(crot)3(H2O)2]2 dimers (crot is crotonate or but‐2‐enoate; Ln is the lanthanide cation), built up around inversion centres and completed by 2,6‐diaminopurine molecules. The lanthanide cation is coordinated by three chelating crotonate units and two water molecules. One of the chelating carboxylate groups acts also in a bridging mode sharing one O atom with both cations and the final result is a pair of DyO9 tricapped prismatic polyhedra linked to each other through a central (Dy—O)2 loop. A feature of the structures is the existence of a complex intermolecular interaction scheme involving two sets of tightly interlinked non‐intersecting one‐dimensional structures, one of them formed by the [Dy(crot)3(H2O)2]2 dimers (running along [100] and linked by O—H...O hydrogen bonds) and the second formed by 2,6‐diaminopurine molecules (evolving along [010] linked by N—H...N hydrogen bonds). 相似文献
16.
Meng Wen Zu‐Ping Xiao Chun‐Ya Wang Xi‐He Huang 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(2):136-139
The title compound, {[Zn4(C8H4O4)3(OH)2(C12H6N2O2)2]·2H2O}n, has been prepared hydrothermally by the reaction of Zn(NO3)2·6H2O with benzene‐1,4‐dicarboxylic acid (H2bdc) and 1,10‐phenanthroline‐5,6‐dione (pdon) in H2O. In the crystal structure, a tetranuclear Zn4(OH)2 fragment is located on a crystallographic inversion centre which relates two subunits, each containing a [ZnN2O4] octahedron and a [ZnO4] tetrahedron bridged by a μ3‐OH group. The pdon ligand chelates to zinc through its two N atoms to form part of the [ZnN2O4] octahedron. The two crystallographically independent bdc2− ligands are fully deprotonated and adopt μ3‐κO:κO′:κO′′ and μ4‐κO:κO′:κO′′:κO′′′ coordination modes, bridging three or four ZnII cations, respectively, from two Zn4(OH)2 units. The Zn4(OH)2 fragment connects six neighbouring tetranuclear units through four μ3‐bdc2− and two μ4‐bdc2− ligands, forming a three‐dimensional framework with uninodal 6‐connected α‐Po topology, in which the tetranuclear Zn4(OH)2 units are considered as 6‐connected nodes and the bdc2− ligands act as linkers. The uncoordinated water molecules are located on opposite sides of the Zn4(OH)2 unit and are connected to it through hydrogen‐bonding interactions involving hydroxide and carboxylate groups. The structure is further stabilized by extensive π–π interactions between the pdon and μ4‐bdc2− ligands. 相似文献
17.
Jeffrey A. Rood Ashley M. Landis Daniel R. Forster Timothy Goldkamp Allen G. Oliver 《Acta Crystallographica. Section C, Structural Chemistry》2016,72(12):990-996
There are challenges in using magnesium coordination complexes as reagents owing to their tendency to adopt varying aggregation states in solution and thus impacting the reactivity of the complexes. Many magnesium complexes are prone to ligand redistribution via Schlenk equilibrium due to the ionic character within the metal–ligand interactions. The role of the supporting ligand is often crucial for providing stability to the heteroleptic complex. Strategies to minimize ligand redistribution in alkaline earth metal complexes could include using a supporting ligand with tunable sterics and electronics to influence the degree of association to the metal atom. Magnesium bis(hexamethyldisilazide) was reacted with salicylaldimines [1L = N‐(2,6‐diisopropylphenyl)salicylaldimine and 2L = 3,5‐di‐tert‐butyl‐N‐(2,6‐diisopropylphenyl)salicylaldimine] in either nondonor (toluene) or donor solvents [tetrahydrofuran (THF) or pyridine]. The structures of the magnesium complexes were studied in the solid state via X‐ray diffraction. In the nondonor solvent, i.e. toluene, the heteroleptic complex bis{μ‐2‐[(2,6‐diisopropylphenyl)iminomethyl]phenolato}‐κ3N,O:O;κ3O:N,O‐bis[(hexamethyldisilazido‐κN)magnesium(II)], [Mg2(C19H22NO)2(C6H18NSi2)2] or [1LMgN(SiMe3)2]2, (1), was favored, while in the donor solvent, i.e. pyridine (pyr), the formation of the homoleptic complex {2,4‐di‐tert‐butyl‐6‐[(2,6‐diisopropylphenyl)iminomethyl]phenolato‐κ2N,O}bis(pyridine‐κN)magnesium(II) toluene monosolvate, [Mg(C27H38NO)2(C5H5N)2]·C5H5N or [{2L2Mg2(pyr)2}·pyr], (2), predominated. Heteroleptic complex (1) was crystallized from toluene, while homoleptic complexes (2) and the previously reported [1L2Mg·THF] [Quinque et al. (2011). Eur. J. Inorg. Chem. pp. 3321–3326] were crystallized from pyridine and THF, respectively. These studies support solvent‐dependent ligand redistribution in solution. In‐situ1H NMR experiments were carried out to further probe the solution behavior of these systems. 相似文献
18.
Zhi-Liang Zhang Jia-Cheng Liu 《Acta Crystallographica. Section C, Structural Chemistry》2016,72(5):389-392
The design and synthesis of new organic lgands is important to the rapid development of coordination polymers (CPs). However, CPs based on asymmetric ligands are still rare, mainly because such ligands are usually expensive and more difficult to synthesize. The new asymmetric ligand 4‐[4‐(1H‐imidazol‐1‐yl)phenyl]pyridine (IPP) has been used to construct the title one‐dimensional coordination polymer, catena‐poly[[[aqua{4‐[4‐(1H‐imidazol‐1‐yl‐κN3)phenyl]pyridine}cadmium(II)]‐μ‐5‐hydroxybenzene‐1,3‐dicarboxylato‐κ3O1,O1′:O3] monohydrate], {[Cd(C8H4O5)(C14H11N3)2(H2O)]·H2O}n, under hydrothermal reaction of IPP with CdII in the presence of 5‐hydroxyisophthalic acid (5‐OH‐H2bdc). The CdII cation is coordinated by two N atoms from two distinct IPP ligands, three carboxylate O atoms from two different 5‐OH‐bdc2− dianionic ligands and one water O atom in a distorted octahedral geometry. The cationic [Cd(IPP)2]2+ nodes are linked by 5‐OH‐bdc2− ligands to generate a one‐dimensional chain. These chains are extended into a two‐dimensional layer structure via O—H…O and O—H…N hydrogen bonds and π–π interactions. 相似文献
19.
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
20.
Neil M. Boag Kathleen M. Coward Anthony C. Jones Martyn E. Pemble J. Robin Thompson 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(12):1438-1439
The hydrolysis product [Ga2(C3H7)4(OH)2]·C14H32N4, derived from the tetrakis(triisopropylgallium)–1,4,8,11‐tetramethyl‐1,4,8,11‐tetraazacyclotetradecane (1/1) adduct, consists of a centrosymmetric [iPr2Ga(μ‐OH)]2 unit hydrogen bonded through the hydroxyl group to a nitrogen on an adjacent centrosymmetric 1,4,8,11‐tetramethyl‐1,4,8,11‐tetraazacyclotetradecane molecule, resulting in the generation of a molecular chain through the crystal. 相似文献