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1.
Preparation of Tetramethylammonium Azidosulfite and Tetramethylammonium Cyanate Sulfur Dioxide‐Adduct, [(CH3)4N]+[SO2N3]–, [(CH3)4N]+[SO2OCN]– and Crystal Structure of [(CH3)4N]+[SO2N3]– Tetramethylammonium azide forms with sulfur dioxide an azidosulfite salt. It is characterized by NMR and vibrational spectroscopy and the crystal structure analysis. [(CH3)4N]+[SO2N3]– crystallizes in the monoclinic space group P21/c with a = 551.3(1) pm, b = 1095.2(1) pm, c = 1465.0(1) pm, β = 100.63(1)°, and four formula units in the unit cell. The crystal structure possesses a strong S–N interaction between the N3– anions and the SO2 molecules. The S–N distance of 200.5(2) pm is longer than a covalent single S–N bond. The structure is compared with ab initio calculated data. Furthermore an adduct of tetrametylammonium cyanate and sulfur dioxide is reported. It is characterised by NMR and vibrational spectroscopy. The structure is calculated by ab initio methods. 相似文献
2.
Yu‐An Xiong Tai‐Ting Sha Qiang Pan Xian‐Jiang Song Shu‐Rong Miao Zheng‐Yin Jing Zi‐Jie Feng Yu‐Meng You Ren‐Gen Xiong 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(26):8949-8953
The X‐site ion in organic–inorganic hybrid ABX3 perovskites (OHPs) varies from halide ion to bridging linkers like HCOO?, N3?, NO2?, and CN?. However, no nitrite‐based OHP ferroelectrics have been reported so far. Now, based on non‐ferroelectric [(CH3)4N][Ni(NO2)3], through the combined methodologies of quasi‐spherical shape, hydrogen bonding functionality, and H/F substitution, we have successfully synthesized an OHP ferroelectric, [FMeTP][Ni(NO2)3] (FMeTP=N‐fluoromethyl tropine). As an unprecedented nitrite‐based OHP ferroelectric, the well‐designed [FMeTP][Ni(NO2)3] undergoes the ferroelectric phase transition at 400 K with an Aizu notation of 6/mmmFm, showing multiaxial ferroelectric characteristics. This work is a great step towards not only enriching the molecular ferroelectric families but also accelerating the potential practical applications. 相似文献
3.
J. Weiss 《无机化学与普通化学杂志》1985,521(2):44-50
Metal Sulfur Nitrogen Compounds 18. Reaction Products of S7NH with Nickel and Copper Salts. Preparation and Structures of the Complexes [Ch34N][Ni(S3N)(CN)2], [(C6H5)4As][Cu(S3N)2], and [(C6H5)4AS][Cu(S3N)Cl]. In the presence of MOH (M = K, [(CH3)4N]), S7NH reacts with Ni(CN)2 to yield, besides the three-nuclear complex M[(S3NNi)3S2], the new mononuclear complex M[Ni(S3N)(CN)2]. The [(CH3)4N]+ salt is monoclinic, C2/m, a = 19.303(9), b =6.941(3), c=16.309(10) Å, β = 144.510(2), Z = 4. The [Ni(S3N)(CN)2]- anion is planar, Ni being coordinated by one S3N? chelate ligand and by two CN? ions. From the reaction of CuCI2, S7NH, and [Ph4As]OH result the salts [Ph4As][Cu(S3N)2] or [Ph4As][Cu(S3N)Cl], depending on the reaction conditions. [Ph4As][Cu(S3N)2] is triclinic, P&1macr;, a = 7.073(3), b = 11.742(4), c = 16.439(6) Å α = 91.08°(3), β = 99.01°(3), γ = 91.58°(3), Z = 2. Two S3N? chelate ligands coordinate to CuI in a distorted tetrahedral arrangement. [Ph4As][Cu(S3N)Cl] is monoclinic, C2/c, a = 17.174(6), b = 13.650(5), c = 21.783(5) Å β = 100.45°(2), Z = 8. CuI is coordinated by one S3N? chelate ligand and one C1?, resulting in a trigonal planar environment. 相似文献
4.
3‐Rhoda‐1,2‐diazacyclopentanes: A Series of Novel Metallacycle Complexes Derived From CN Functionalization of Ethylene
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Marcus W. Drover Daniel W. Beh Prof. Dr. Pierre Kennepohl Prof. Dr. Jennifer A. Love 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13345-13355
Rh‐containing metallacycles, [(TPA)RhIII(κ2‐(C,N)‐CH2CH2(NR)2‐]Cl; TPA=N,N,N,N‐tris(2‐pyridylmethyl)amine have been accessed through treatment of the RhI ethylene complex, [(TPA)Rh(η2‐CH2CH2)]Cl ([ 1 ]Cl) with substituted diazenes. We show this methodology to be tolerant of electron‐deficient azo compounds including azo diesters (RCO2N?NCO2R; R=Et [ 3 ]Cl, R=iPr [ 4 ]Cl, R=tBu [ 5 ]Cl, and R=Bn [ 6 ]Cl) and a cyclic azo diamide: 4‐phenyl‐1,2,4‐triazole‐3,5‐dione (PTAD), [ 7 ]Cl. The latter complex features two ortho‐fused ring systems and constitutes the first 3‐rhoda‐1,2‐diazabicyclo[3.3.0]octane. Preliminary evidence suggests that these complexes result from N–N coordination followed by insertion of ethylene into a [Rh]?N bond. In terms of reactivity, [ 3 ]Cl and [ 4 ]Cl successfully undergo ring‐opening using p‐toluenesulfonic acid, affording the Rh chlorides, [(TPA)RhIII(Cl)(κ1‐(C)‐CH2CH2(NCO2R)(NHCO2R)]OTs; [ 13 ]OTs and [ 14 ]OTs. Deprotection of [ 5 ]Cl using trifluoroacetic acid was also found to give an ethyl substituted, end‐on coordinated diazene [(TPA)RhIII(κ2‐(C,N)‐CH2CH2(NH)2‐]+ [ 16 ]Cl, a hitherto unreported motif. Treatment of [ 16 ]Cl with acetyl chloride resulted in the bisacetylated adduct [(TPA)RhIII(κ2‐(C,N)‐CH2CH2(NAc)2‐]+, [ 17 ]Cl. Treatment of [ 1 ]Cl with AcN?NAc did not give the Rh?N insertion product, but instead the N,O‐chelated complex [(TPA)RhI ( κ2‐(O,N)‐CH3(CO)(NH)(N?C(CH3)(OCH?CH2))]Cl [ 23 ]Cl, presumably through insertion of ethylene into a [Rh]?O bond. 相似文献
5.
An A‐Site Mixed‐Ammonium Solid Solution Perovskite Series of [(NH2NH3)x(CH3NH3)1−x][Mn(HCOO)3] (x=1.00–0.67)
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Sa Chen Ran Shang Prof. Bing‐Wu Wang Prof. Zhe‐Ming Wang Prof. Song Gao 《Angewandte Chemie (International ed. in English)》2015,54(38):11093-11096
The A‐site mixed‐ammonium solid solutions of metal–organic perovskites [(NH2NH3)x(CH3NH3)1?x][Mn(HCOO)3] (x=1.00–0.67) exhibit para‐ to ferroelectric diffuse phase transitions with lowered transition temperatures from x=1.00 to 0.67. These properties are due to the decreased framework distortion and polarization in their low temperature ferroelectric phases caused by the increased CH3NH3+ concentration. 相似文献
6.
Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXXIV. Synthesis and Properties of 3-(N,N-dialkylamino)propyl Manganese Compounds MnCl2 reacts with lithium organyls of the type R2N(CH2)3Li with formation of definite organomanganese complexes. The pure [(CH3)2N(CH2)3]2Mn, [(C2H5)2N(CH2)3]2Mn, [(CH2)5N(CH2)3]2Mn and the complexes [(CH3)2N(CH2)3]2Mn · LiCl and Li{Mn[(CH2)3N(CH3)2]3} · 1,5 THF were isolated. [(CH3)2N(CH2)3]2Mn · 2 Li(acac) was obtained as a result of reactions of Mn(acac)2 and Mn(acac)3 with the corresponding lithium organyl. The σ-organomanganese(II) derivatives were characterized in detail by elementary analysis, molecular weight determination, ESR- and IR-spectra, conductivity measurements and the magnetic moments. 相似文献
7.
Bis(tetramethylammonium) dodecahydrododecaborate, [(CH3)4N]2[B12H12], and bis(tetramethylammonium) dodecahydrododecaborate acetonitrile, [(CH3)4N]2[B12H12] · CH3CN, were synthesized and characterized via Infrared, 1H and 11B NMR spectroscopy. [(CH3)4N]2[B12H12] crystallizes isopunctual to the alkali metal dodecaborates. The crystal structure of [(CH3)4N]2[B12H12] · CH3CN was determined from single crystal data and refined in the orthorhombic crystal system (Pcmn, no. 62, a = 898.68(8), b = 1312.85(9) c = 1994.5(1) pm, R(|F| , 4σ) = 5.9%, wR(F2) = 18.3%). Here, the geometry of the dodecaborate anion is that of an almost ideal icosahedron, less distorted than most other dodecaborates known. By low‐temperature Guinier‐Simon diffractometry phase transitions were detected for [(CH3)4N]2[B12H12] and [(CH3)4N]2[B12H12] · CH3CN at –70 and –15 °C, respectively. 相似文献
8.
The Molybdenum(V) and Tungsten(VI) Oxoazides [MoO(N3)3], [MoO(N3)3⋅2 CH3CN], [(bipy)MoO(N3)3], [MoO(N3)5]2−, [WO(N3)4], and [WO(N3)4⋅CH3CN]
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Prof. Dr. Ralf Haiges Juri Skotnitzki Zongtang Fang Prof. Dr. David A. Dixon Prof. Dr. Karl O. Christe 《Angewandte Chemie (International ed. in English)》2015,54(51):15550-15555
A series of novel molybdenum(V) and tungsten(VI) oxoazides was prepared starting from [MOF4] (M=Mo, W) and Me3SiN3. While [WO(N3)4] was formed through fluoride–azide exchange in the reaction of Me3SiN3 with WOF4 in SO2 solution, the reaction with MoOF4 resulted in a reduction of MoVI to MoV and formation of [MoO(N3)3]. Carried out in acetonitrile solution, these reactions resulted in the isolation of the corresponding adducts [MoO(N3)3?2 CH3CN] and [WO(N3)4?CH3CN]. Subsequent reactions of [MoO(N3)3] with 2,2′‐bipyridine and [PPh4][N3] resulted in the formation and isolation of [(bipy)MoO(N3)3] and [PPh4]2[MoO(N3)5], respectively. Most molybdenum(V) and tungsten(VI) oxoazides were fully characterized by their vibrational spectra, impact, friction and thermal sensitivity data and, in the case of [WO(N3)4?CH3CN], [(bipy)MoO(N3)3], and [PPh4]2[MoO(N3)5], by their X‐ray crystal structures. 相似文献
9.
Synthesis and Crystal Structure of the Heterobimetallic Diorganotindichloride (FcN, N)2SnCl2 (FcN, N—: (η5‐C5H5)Fe{η5‐C5H3[CH(CH3)N(CH3)CH2CH2NMe2]‐2}—) The heterobimetallic title compound [(FcN, N)2SnCl2] ( 1 ) was obtained by the reaction of [LiFcN, N] with SnCl4 in the molar ratio 1:1 in diethylether as a solvent. The two FcN, N— ligands in 1 are bound to Sn through a C‐Sn σ‐bond; the amino N atoms of the side‐chain in FcN, N— remain uncoordinated. The crystals contain monomeric molecules with a pseudo‐tetrahedral coordination at the Sn atom: Space group P21/c; Z = 4, lattice dimensions at —90 °C: a = 9.6425(2), b = 21.7974(6), c = 18.4365(4) Å, β = 100.809(2)°, R1obs· = 0.051, wR2obs· = 0.136. 相似文献
10.
The Crystal Structure of cis‐ and trans‐N‐iso‐Propylamidodimethyl Indium, [(CH3)2In‐N(H)iC3H7]2 According to the X‐ray structure determination [(CH3)2In‐N(H)iC3H7]2 (prepared from InMe3 (Me = CH3) and H2NiPr (iPr = CH(CH3)2) crystallizes in the monoclinic space group P21/n with 3 dimeric trans as well as 3 dimeric cis isomers per unit cell. The centrosymmetric form has a planar In2N2 core with In—N bonds of 222.1(4) and 222.9(5) pm, respectively, the skeleton of the cis isomer with In—N bonds of 221.4(4) pm is slightly folded (13.7°). Some 1H, 13C NMR, IR, and Raman data are reported. 相似文献
11.
《Radiation Physics and Chemistry》1999,53(5):501-504
Gamma irradiation damage centres in (CH3)3NHClO4, (CH3)3NHBF4 and [(CH3)4N]2ZnCl4 were investigated by electron paramagnetic resonance spectroscopy at room temperature. The centres were found to be (CH3)3N+. and the hyperfine structure parameters for methyl protons and the nitrogen nucleus were determined. The results indicated that the (CH3)3N+. radical wholly performs reorientational motions around its C3v axis in addition to the reorientatonal motions of the methyl groups around their C3v axes. These results were compared with the earlier studies on (CH3)3N+. radical and discussed. Low temperature measurements on the first two of the title compounds were assessed. 相似文献
12.
An Unusual Phase Transition Driven by Vibrational Entropy Changes in a Hybrid Organic–Inorganic Perovskite
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Wenjuan Wei Prof. Wei Li Dr. Keith T. Butler Dr. Guoqiang Feng Prof. Christopher J. Howard Prof. Michael A. Carpenter Prof. Peixiang Lu Prof. Aron Walsh Prof. Anthony K. Cheetham 《Angewandte Chemie (International ed. in English)》2018,57(29):8932-8936
The driving forces for the phase transitions of ABX3 hybrid organic–inorganic perovskites have been limited to the octahedral tilting, order–disorder, and displacement. Now, a complex structural phase transition has been explored in a HOIP, [CH3NH3][Mn(N3)3], based on structural characterizations and ab initio lattice dynamics calculations. This unusual first‐order phase transition between two ordered phases at about 265 K is primarily driven by changes in the collective atomic vibrations of the whole lattice, along with concurrent molecular displacements and an unusual octahedral tilting. A significant entropy difference (4.35 J K?1 mol?1) is observed between the low‐ and high‐temperature structures induced by such atomic vibrations, which plays a main role in driving the transition. This finding offers an alternative pathway for designing new ferroic phase transitions and related physical properties in HOIPs and other hybrid crystals. 相似文献
13.
Prof. Dr. Ralf Haiges Monica Vasiliu Prof. Dr. David A. Dixon Prof. Dr. Karl O. Christe 《Angewandte Chemie (International ed. in English)》2015,54(31):9101-9105
Vanadium(V) oxoazide [VO(N3)3] was prepared through a fluoride–azide exchange reaction between [VOF3] and Me3SiN3 in acetonitrile solution. When the highly impact‐ and friction‐sensitive compound [VO(N3)3] was reacted with 2,2′‐bipyridine, the adduct [(bipy)VO(N3)3] was isolated. The reaction of [VO(N3)3] with [PPh4]N3 resulted in the formation and isolation of the salt [PPh4]2[VO(N3)5]. The adduct [(bipy)VO(N3)3] and the salt [PPh4]23[VO(N3)5] were characterized by vibrational spectroscopy and single‐crystal X‐ray structure determination, making these compounds the first structurally characterized vanadium(V) azides. 相似文献
14.
The new manganese tetraphosphonate, Mn[(HO3PCH2)2N(H)(CH2)4(H)N(CH2PO3)2] (1) was hydrothermally synthesized from MnCl2 and N,N,N′,N′-tetrametylphosphono-1,4-diaminobutane, (H2O3PCH2)2N-(CH2)4-N(CH2PO3H2)2. The structure was determined from single-crystal X-ray diffraction data (Mn[(HO3PCH2)2N(H)(CH2)4(H)N(CH2PO3)2], monoclinic, P21/a, with a=9.6663(1), b=9.2249(2), c=10.5452(1) pm, β=105.676(1)°, V=905.35(3)×106 pm, Z=2, R1=0.051, wR2=0.109 (all data). The structure contains the zwitter ions [(HO3PCH2)2N(H)-(CH2)4-(H)N(CH2PO3)2]2− and is built from alternating corner-linked [MnO6] and [PO3C] polyhedra forming a two-dimensional net of eight-rings. These layers are connected to a pillared structure by the diaminobutane groups. Magnetic susceptibility data confirms the presence of Mn2+ ions. Thermogravimetric measurements show a stability of 1 up to ∼290°C. Between 290°C and 345°C a one-step loss of ∼7.0% is observed, and above 345°C the continuous decomposition of the organic part of the structures takes place. 相似文献
15.
Studies of Polyhalides. 22. On Dimethyldiphenylammoniumpolyiodides (Me2Ph2N)In with n = 3, 13/3, 6, and 8: Preparation and Crystal Structures of a Triiodide (Me2Ph2N)I3, Tridecaiodide (Me2Ph2N)3I13, Dodecaiodide (Me2Ph2N)2I12, and Hexadecaiodide (Me2Ph2N)2I16 The new compounds [(CH3)2(C6H5)2N]I3, [(CH3)2(C6H5)2N]3I13, [(CH3)2(C6H5)2N]2I12 and [(CH3)2(C6H5)2N]2I16 have been prepared by the reaction of dimethyldiphenylammonium iodide [(CH3)2(C6H5)2N]I with iodine I2 in ethanol. Their crystal structures have been determined by single crystal X-ray diffraction methods. The structure of the triiodide may be described as a layerlike packing of pairs of nearly linear symmetric anions and tetraedral cations. The tridecaiodide forms zig-zag chains of iodide ions and iodine molecules with the iodide ion also weakly coordinated by two pentaiodide groups. The dodecaiodide is built from two pentaiodide-groups, which are bridged by an iodine molecule and connected with secondary bonds forming double chains. The hexadecaiodide ion forms layers built up from two heptaiodide groups and one iodine molecule. Thus the dimethyldiphenylammonium cation stabilizes a unique series of polyiodides of extraordinary composition and structure. 相似文献
16.
Diego da S. Padilha Adailton J. Bortoluzzi Marciela Scarpellini 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(1):17-22
A novel Ni2+ complex with the N4‐donor tripodal ligand bis[(1‐methyl‐1H‐imidazol‐2‐yl)methyl][2‐(pyridin‐2‐yl)ethyl]amine (L), namely, aqua{bis[(1‐methyl‐1H‐imidazol‐2‐yl‐κN3)methyl][2‐(pyridin‐2‐yl‐κN)ethyl]amine‐κN}chloridonickel(II) perchlorate, [NiCl(C17H22N6)(H2O)]ClO4 or [NiCl(H2O)(L)Cl]ClO4 ( 1 ), was synthesized and characterized by spectroscopic and spectrometric methods. The crystal structure of 1 reveals an interesting and unusual cocrystallization of isomeric complexes, which are crystallographically disordered with partial occupancy of the labile cis aqua and chloride ligands. The Ni2+ centre exhibits a distorted octahedral environment, with similar bond lengths for the two Ni—N(imidazole) bonds. The bond length increases for Ni—N(pyridine) and Ni—N(amine), which is in agreement with literature examples. The bond lengths of the disordered labile sites are also in the expected range and the Ni—Cl and Ni—O bond lengths are comparable with similar compounds. The electronic, redox and solution stability behaviour of 1 were also evaluated, and the data obtained suggest the maintenance of structural integrity, with no sign of demetalation or decomposition under the studied conditions. 相似文献
17.
Synthesis and Characterization of Tricarbastannatranes and Their Reactivity in B(C6F5)3‐Promoted Conjugate Additions
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Azadeh Kavoosi Prof. Eric Fillion 《Angewandte Chemie (International ed. in English)》2015,54(18):5488-5492
The synthesis and characterization of a series of tricarbastannatranes, in the solid state and in solution, are described. The structures of the complexes [N(CH2CH2CH2)3Sn](BF4), [N(CH2CH2CH2)3Sn](SbF6), [N(CH2CH2CH2)3Sn]4[(SbF6)3Cl], and [(N(CH2CH2CH2)3Sn)2OH][MeB(C6F5)3] were determined by X‐ray crystallography. Furthermore, the B(C6F5)3‐promoted conjugate addition of alkyl‐tricarbastannatranes to benzylidene derivatives of Meldrum’s acid was investigated, and detailed mechanistic studies are presented. 相似文献
18.
α-Si3N4 is synthesized by an ammonia thermal synthesis using a cyclic oligosilazane, [(CH3)2SiNH]4, as the starting material. [(CH3)2SiNH]4 reacts in the presence of ammonia at 900°C and 80 MPa pressure to give silicon nitride imide (Si2N2NH). Subsequently, Si2N2NH is converted into α-Si3N4 by thermal decomposition at 1500°C and 0.1 MPa nitrogen with the simultaneous loss of NH3. 相似文献
19.
Synthesis,Structures, and Magnetic Properties of Chiral One‐dimensional CrIII‐MnIII Heterobimetallic Complexes Based on [(Tp)Cr(CN)3]–
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Two CrIII‐MnIII heterobimetallic compounds, [Mn((R,R)‐5‐MeOSalcy)Cr(Tp)(CN)3 · 2CH3CN]n ( 1‐RR ) and [Mn((S,S)‐5‐MeOSalcy)Cr(Tp)(CN)3·2CH3CN]n ( 1‐SS ) [Salcy = N,N′‐(1,2‐cyclohexanediylethylene)bis(salicylideneiminato) dianion], were synthesized by using the tricyanometalate building block, [(Tp)Cr(CN)3]– [Tp = tris(pyrazolyl) hydroborate] and chiral MnIII Schiff base precursors. Structural analyses and circular dichroism (CD) spectra revealed that 1‐RR and 1‐SS are a pair of enantiomers containing a neutral cyano‐bridged zigzag chain with (–Cr–C≡N–Mn–N≡C–)n as the repeating unit. Magnetic studies show that antiferromagnetic couplings between CrIII and MnIII ions occur by cyanide bridges. 1‐RR and 1‐SS present metamagnetic, spin‐canting, and antiferromagnetic order behaviors at low temperatures. 相似文献
20.
Heterobimetallic Complexes of Lithium, Aluminum, and Gold with the N ‐[2‐ N ′, N ′‐(dimethylaminoethyl)‐ N ‐methyl‐aminoethyl]‐ferrocenyl Ligand (η5‐C5H5)Fe{η5‐C5H3[CH(CH3)N(CH3)CH2CH2NMe2]‐2} N‐[2‐N′,N′‐(dimethylaminoethyl)‐N‐methyl‐aminoethyl]ferrocene FcN,NH ( 1 ) reacts with nBuLi under formation of the lithium organyl (FcN,N)Li ( 2 ). At reactions of 2 with AlBr3 and AuCl · PPh3 the heterobimetallic organo derivatives (FcN,N)AlBr2 ( 3 ), (FcN,N)Au · PPh3 ( 4 ) are formed. A detailed characterization of 2 – 4 was carried out by single crystal x‐ray analyses as well as by NMR and Mößbauer spectroscopy. 相似文献