共查询到20条相似文献,搜索用时 31 毫秒
1.
Wen-Feng Liaw Yih-Chern Homg Der-Shiaw Ou Gene-Hsiang Lee Shie-Ming Peng 《中国化学会会志》1993,40(4):367-371
Addition of NOBF4 to fac-[PPN][Fe(CO)3(TePh)3] in THF at ambient temperature results in formation of Fe2(μ-TePh)2(NO)4l Fe2(?TePh)2(CO)6 and organic products. Methylation of fac-[PPN][Fe(CO)3- (TePh)3] by Mel or [Me3O][BF4] leads to the known dimer Fe2(μ.-TePh)2(CO)6 and organic products. Fe2(μ-TePh)2(NO)4 crystallizes in the orthorhombic space group P bca, with a = 12.701(5) Å, b = 6.7935(16) Å, c = 21.299(9) Å, V = 1837.8(11) Å3, and Z = 4. The core geometry of Fe2(μ-TePh)2(NO)4 is best described as a Fe2Te2 planar rhombus with Te-Fe-Te bond angle 112.09(4)°. A Fe-Fe bond (length 2.827(2) Å) is proposed for Fe2(μ-TePh)2(NO)4 on the basis of the 18-electron rule. The iron atom adopts a distorted tetrahedral geometry with acute bridge Fe-Te-Fe angles 67.91(3)°, and bridging Fe-Te bond of length 2.53(1) Å. 相似文献
2.
Wen-Feng Liaw Chao-Yi Ching Chen-Kang Lee Gene-Hsiang Lee Shie-Ming Peng 《中国化学会会志》1996,43(5):427-431
Oxidative addition of diphenyl disulfide to the coordinatively unsaturated [Mn(CO)5]? led to the formation of low-spin, six-coordinate cis-[Mn(CO)4(SPh)2]?. The complex cis-[PPN][Mn(CO)4(SPh)2] crystallized in monoclinic space group P21/c with a = 9.965(2) Å, b = 24.604(5) Å, c = 19.291(4) Å, β = 100.05(2)°, V = 4657(2)Å3, and Z = 4; final R = 0.036 and Rw = 0.039. Thermal transformation of cis-[Mn(CO)4(SPh)2]? to [(CO)3Mn(μ-SPh)3Mn(CO)3]? was completed overnight in THF at room temperature. Additionally, reaction of [Mn(CO)5]? and PhSH in 1:2 mole ratio also led to cis-[PPN](Mn(CO)4(SPh)2]. Presumably, oxidative addition of PhSH to [Mn(CO)4]? was followed by a Lewis acid-base reaction to form cis-[Mn(CO)4(SPh)2]? with evolution of H2. 相似文献
3.
Anionic iron(0) tetracarbonyl with terminal phenyltellurolate ligand PhTe?, [PhTeFe(CO)4]?, has been synthesized and characterized. The title compound was obtained by addition of (PhTe)2 to [PPN][HFe(CO)4] THF solution dropwise. [PPN][PhTeFe(CO)4] crystallizes in the monoclinic space group C c, with a = 16.119(4) Å, b = 13.141(3) Å, c = 19.880(8) Å, β = 93.04(3)°, V = 4205(2) Å3, and Z = 4. The [PhTeFe(CO)4]? anion is a trigonal-bipyramidal complex in which the phenyltellurolate ligand occupies an axial position with Fe-Te bond length 2.630(5) Å and the Fe-Te-C(Ph) angle is 103.4(5)°. The neutral iron(0)-telluroether compound, (PhTeMe)Fe(CO)4, was prepared by alkylation of the [PhTeFe(CO)4]?. Protonation of [PhTeFe(CO)4]?and reaction of H2Fe(CO)4 and PhTe)2 ultimately lead to formation of the known dimer Fe2(μ-TePh)2(CO)6 and H2. 相似文献
4.
Wen-Feng Liaw Chia-Huei Lai Ming-Hsi Chiang Cheng-Kang Hsieh Gcne-Hsiang Lee Shie-Ming Peng 《中国化学会会志》1993,40(5):437-444
Diphenyldichalcogenides (PhE)2 (E = Te, Se) react with Fe(0)-phenylchalcogenolate [PPN] [PhEFe(CO)4] to yield the products of oxidative addition, Fe(II)-mixed-phenylchalcogenolate fac- [PPN][Fe(CO)3(TePh)n(ScPh)3-n] (n = 1, 2). Reactions of [PPN][REFe(CO)4] (E=Se, R=Me; E=S, R=Et) and diphenyldichalcogenides yielded ligand-exchange products [PPN][PhEFe(CO)4] (E=Te, Se, S). The compounds [Fe(CO)3(TePh)(ScPh)2]? (l) and [Fe(CO)3(TePh)2 (2) crystallize in the isomorphous monoclinic space group C2/e, with a = 32.035(8), b = 11.708(6), c = 28.909(6) Å, Z = 8, R = 0.048, and Rw = 0.044 (1); with a = 32.089(5), b= 11.745(2), c = 28.990(8) Å, Z = 8, R = 0.048, and Rw = 0.048 (2). The complexes 1 and 2 crystallize as discrete cations of PPN+ and anions of [Fe(CO)3(TcPh)u(ScPh)3-n] (n=1, 2), and one half solvent molecule THF. The geometry around Fe(II) is a distorted octahedron with three carbonyl groups and three phenylchalcogenolate ligands occupying facial positions. 相似文献
5.
Wen-Feng Liaw Yih-Chern Horng Der-Shiaw On Chin-Yuan Chuang Chen-Kang Lee Gene-Hsiang Lee Shie-Ming Peng 《中国化学会会志》1995,42(1):59-65
The monomeric rhenium(I) complex with bidentate telluroether ligand Re(CO)3Br(PhTe(CH2)3TePh) (1) was accessible via reaction of the PhTe(CH2)3TePh with Re(CO)5Br. This chelate complex crystallized in triclinic space group $ {\rm P}\bar 1 $ with a = 9.390(5) Å, b = 10.961(3) Å, c = 11.849(4) Å a = 63.30(3)°, β = 87.49(4)° γ = 69.31(4)°, V = 1009.5(7) Å3 Z = 2, R = 0.033, and Rw = 0.034. Reaction of Re(CO)5Cl with NaTePh yielded the Re(I) specics PhTeRe(CO)5 (2). This complex crystallized in triclinic space group $ {\rm P}\bar 1 $ with a = 7.085(1) Å, b = 9.203(1) Å, c = 11.341(1) Å, α = 107.24(1)°, β = 100.56(1)°, γ = 96.47(1)°, V = 683.2(2) Å3, Z = 2, R = 0.027, Rw = 0.022. Reaction of PhTeRe(CO)5 and (PhSe)2 in THF at 65 °C yielded a product that was confirmed crystallographically to be the known species Re2(μ-SePh)2(CO)8 (3), in which two phenylselenolate ligands bridge the two Re(I). Compound 3 crystallized in monoclinic space group P21/n with a = 7.210(2) Å, b = 18.862(6) Å, c = 9.083(3) Å, β = 107.48(3)° V = 1178.2(7) Å3, Z = 2, R = 0.046, and Rw = 0.051. Methylation of PhTeRe(CO)5 with [Me3O][BF4] afforded Re(I) product [(PhTeMe)Re(CO)5][BF4] (4). This monodentate telluroether species crystallized in monoclinic space group P21/n with a = 8.405(1) Å, b = 13.438(3) Å, c = 15.560(2) Å, β = 92.59(1)° V = 1755.5(5) Å3, Z = 4, R = 0.035, and Rw = 0.035. 相似文献
6.
Chien‐Kuo Hsieh Feng‐Chun Lo Gene‐Hsiang Lee Shie‐Ming Peng Wen‐Feng Liaw 《中国化学会会志》2000,47(1):103-107
Complex fac‐[Fe(CO)3(TePh)3]? was employed as a “metallo chelating” ligand to synthesize the neutral (CO)3Mn(μ‐TePh)3Fe(CO)3 obtained in a one‐step synthesis by treating fac‐[Fe(CO)3(TePh)3]? with fac‐[Mn‐(CO)3(CH3CN)3]+. It seems reasonable to conclude that the d6 Fe(II) [(CO)3Fe(TePh)3]? fragment is isolobal with the d6 Mn(I) [(CO)3Mn(TePh)3]2? fragment in complex (CO)3Mn(μ‐TePh)3Fe(CO)3. Addition of fac‐[Fe(CO)3(TePh)3]? to the CpNi(I)(PPh3) in THF resulted in formation of the neutral CpNi(TePh)(PPh3) also obtained from reaction of CpNi(I)(PPh3) and [Na][TePh] in MeOH. This investigation shows that fac‐[Fe(CO)3(TePh)3]? serves as a tridentate metallo ligand and tellurolate ligand‐transfer reagent. The study also indicated that the fac‐[Fe(CO)3(SePh)3]? may serve as a better tridentate metallo ligand and chalcogenolate ligand‐transfer reagent than fac‐[Fe(CO)3(TePh)3]? in the syntheses of heterometallic chalcogenolate complexes. 相似文献
7.
Reactions of Cyclostibanes, (RSb)n [R = (Me3Si)2CH, n = 3; Me3CCH2, n = 4, 5] with the Transition Metal Carbonyl Complexes [W(CO)5(thf)], [CpxMn(CO)2(thf)], [CpxCr(CO)3]2, and [Co2(CO)8]; Cpx = MeC5H4 (RSb)3 [R = (Me3Si)2CH] reacts with [W(CO)5(thf)], [CpxMn(CO)2(thf)], or [Co2(CO)8] to give [(RSb)3W(CO)5] ( 1 ), [RSb{Mn(CO)2Cpx}2] ( 2 ) or [RSbCo(CO)3]2 ( 3 ). The reaction of (R′Sb)n (n = 4, 5; R′ = Me3CCH2) with [CpxCr(CO)3]2 leads to [(R′Sb)4{Cr(CO)2Cpx}2] ( 4 ); Cpx = MeC5H4, thf = Tetrahydrofuran. 相似文献
8.
Hsin-Ell Wang Chi-Tsuan Huang Lih-Ming Yiin Ming-Chu Cheng Shie-Ming Peng Shiuh-Tzung Liu 《中国化学会会志》1997,44(4):427-430
Crystal structures of a series of manganese(I) complexes containing tripodal ligands were determined. For [η3-{CH3C(CH2PPh2)2(CH2SPh)-P,P′,S}Mn(CO)3]PF6 ( 1 ): a = 10.856(3) Å, b = 19.698(3) Å, c = 17.596(5) Å, β = 96.17(2)°, monoclinic, Z = 4, P21/c, R(Fo) = 0.068, Rw(Fo) = 0.055 for 3617 reflections with Io > 2σ(Io). For [η3-{CH3C(CH2PPh2)(CH2SPh)2-P,P′,S}Mn(CO)3]PF6 ( 2 ): a = 9.890(2) Å, b = 20.403(4) Å, c = 10.269(3) Å, β = 117.44(2)°, monoclinic, Z = 2, P2l, R(Fo) = 0.050, Rw(Fo) = 0.037 for 1760 reflections with Io > 2σ(Io). For [η3-{CH3C(CH2PPh2)2(CH2S)-P,P′,S}Mn(CO)3] ( 4 ): a = 8.191(7) Å, b = 10.495(3) Å, c = 19.858(6) Å, α = 99.61(2)°, β = 96.17(2)°, γ = 92.70(4)°, triclinic, Z = 2, P-I, R(Fo) = 0.048, Rw(Fo) = 0.039 for 2973 reflections with Io > 2σ(Io). There is no significant difference in the bond lengths of Mn-S bonds among three species in their crystal structures [2.325(2) Å in 1; 2.358(4) in 2; 2.380(2) in 4], but the better donating ability of thiolate in complex 4 appears on the lower frequencies of its carbonyl stretching absorptions. 相似文献
9.
The crystal structure of [Mn(HIDA)2(H2O)2] (Tetragonal, P4¯21c (no.114), a = b = 8.10(2)Å, c = 9.605(3)Å, α = β = γ = 90°, Z = 2, R = 0.051, wR2 = 0.123 for 460 observed reflections) consists of infinite acentric 2D square grids with HIDA— ions as bridging ligands. The 2D grids are interlocked(along the c axis) by hydrogen bonding. The Mn atoms are octahedrally coordinated by four O atoms of four HIDA— ions (d(Mn—O)= 2.183(4)Å ) and two O atoms of two water molecules (d(Mn—OW) = 2.154(5)Å ). The results show that this acentric coordination polymer exhibits strong powder second harmonic generation (SHG) efficiency, ca. 1.9 times that of potassium dihydrogen phosphate, and remarkable thermal stability. 相似文献
10.
Gelson Manzoni de Oliveira Gleison Antonio Casagrande Eliandro Faoro Ramo Marceli Fernandes Jr. Peter Mayer Ernesto Schulz Lang 《无机化学与普通化学杂志》2003,629(9):1566-1568
[BrMn(CO)5] reacts with benzoylhydrazine in THF occurring substitution of two CO groups by a Metal‐ligand ring to give fac‐[Mn(Br)(CO)3(BHD)]·2THF (BHD = C6H5CONHNH2). The novel compound shows a distorted octahedral arrangement at the manganese atom, with three nearly linear carbonyl ligands in a fac arrangement, illustrating another example that the CO group in position trans to the bromine ligand in [BrMn(CO)5] presents the most intensive metal‐CO backbonding effect of all the CO groups of the parent complex, leading to the formation of a facial (and not meridional) isomer, even in the presence of a bidentate ligand like benzydrazide. X‐ray measures of yellow crystals showed that the title complex belong to space group P21/c, with the asymmetric unit containing one crystallographically independent [Mn(Br)(CO)3(BHD)] complex and two tetrahydrofurane solvate molecules. The new compound represents heretofore the unique occurrence of the complexing single bidentate ligand ‐O=C(Ph)‐N(H)‐N(H)2‐ with an octahedral coordination at the MnI atom supported chiefly by carbonyl groups. 相似文献
11.
A. A. Pasynskii S. S. Shapovalov Yu. V. Torubaev I. V. Skabitskii A. V. Pavlova O. A. Tikhonova A. S. Sidorenkov T. A. Krishtop 《Russian Journal of Coordination Chemistry》2014,40(10):697-703
The reaction of CpFe(CO)2TePh (I) with ferricinium hexafluorophosphate as an oxidant affords ionic complex {[CpFe(CO)2]2(μ-TePh)}+PF 6 ? (II) with the simultaneous formation of diphenylditellurium. The decarbonylation of compound II by Me3NO followed by the addition of complex I affords trinuclear complex {[CpFe(CO)2(μ-TePh)]2Fe(CO)Cp}PF6 (III). The corresponding tetrafluoroborate (IV) is synthesized similarly. The heating of compound I with PPh3 gives CpFe(CO)(PPh3)TePh (V) that reacts with ionic complex [CpMn(CO)2(NO)]PF6 (VI) to form binuclear heterometallic ionic complex [CpFe(CO)(PPh3)(μ-TePh)Mn(CO)(NO)Cp]PF6 (VII). A similar reaction of Cp′Fe(CO)2TePh (Cp′ is methylcyclopentadienyl) with compound VI affords heterometallic [Cp′Fe(CO)2(μ-TePh)Mn(CO)(NO)Cp]PF6 (VIII). The structures of compounds II, IV, VII, and VIII are determined by X-ray diffraction analysis (CIF files CCDC 963285, 963286, 963288, and 963289, respectively). 相似文献
12.
The reaction of PPh2Cl with orthomanganated acetophenone, 2′-CH3C(O)C6H4Mn(CO)4, gives Mn2(μ-η1,η1-Ph2PPPh2)(μ-Cl)2(CO)6. An X-ray structure determination [triclinic, space group P1 , a = 10.908(4) Å, b = 11.756(3) Å, c = 12.186(3) Å, α = 96.20(2)°, β = 99.51(2)°, γ = 96.52(2)°] shows two Mn(CO)3 groups held together by two bridging Cl ligands, and further bridged by a Ph2P? PPh2 group prepared in situ. 相似文献
13.
Crystal Structure of (Me4N)3[Ir(SCN)6], Vibrational Spectra and Normal Coordinate Analysis From a mixture of the linkage isomers [Ir(NCS)n(SCN)6–n]3–, n = 0–2, pure [Ir(SCN)6]3– has been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on a single crystal of (Me4N)3[Ir(SCN)6] (trigonal, space group R3, a = 14.838(2), c = 23.827(1) Å, Z = 6) reveals the presence of two crystallographically independent complex anions which C3i symmetry correlates with the cation/anion ratio 3 : 1. The thiocyanate ligands are exclusively S-coordinated with the average Ir–S distance of 2.384 Å and the Ir–S–C angle of 106.4°. The torsion angles S–Ir–S–C are 17.5 and 42.1°. The IR and Raman spectra of the (n-Bu4N) salt are assigned by normal coordinate analysis based on the molecular parameters of the X-ray determination. The valence force constant fd(IrS) is 1.57 mdyn/Å. 相似文献
14.
Preparation, Structures, and EPR Spectra of the Rhenium(II) Thionitrosyl Complexes trans -[Re(NS)Cl3(MePh2P)2] and trans -[Re(NS)Br3(Me2PhP)2] The paramagnetic rhenium(II) thionitrosyl compounds trans-[Re(NS)Cl3(MePh2P)2] and trans-[Re(NS)Br3(Me2PhP)2] are characterized by crystal structure diffraction and EPR spectroscopy. Trans-[Re(NS)Cl3(MePh2P)2] is formed during the reduction of (a) [ReNCl2(MePh2P)3] with disulphur dichloride or (b) of mer-[ReCl3(MePh2P)3] with trithiazyl chloride. Trans-[Re(NS)Br3(Me2PhP)2] is the final product of the ligand exchange reaction of mer-[Re(NS)Cl2(Me2PhP)3] with bromine whereby the metal occurred to be simultaneusly oxidized. The crystal structure analyses show for trans-[Re(NS)Cl3(MePh2P)2] (monoclinic, C2/c, a = 13.831(3) Å, b = 13.970(1) Å, c = 14.682(2) Å, β = 95.33(1), Z = 4) and trans-[Re(NS)Br3(Me2PhP)2] (monoclinic, C2/c, a = 33.292(5) Å, b = 8.697(1) Å, c = 17.495(3) Å, β = 115.65(1), Z = 8) linear co-ordinated NS ligands (Re–N–S-angles 180° and 174.8°). The metal atom is octahedrally co-ordinated with the phosphine ligands in trans position to each other. X-band and Q-band EPR spectra of the rhenium(II) thionitrosyl complexes (5 d5 “low-spin” configuration, S = 1/2) are detected in the temperature range 295 ≥ T ≥ 130 K. They are characterized by well resolved 185,187Re hyperfine patterns. The hyperfine parameters are used to get information about the spin-density distribution of the unpaired electron in the complexes under study. 相似文献
15.
Alan H. Cowley Andreas Decken Claudia A. Olazbal Nicholas C. Norman 《无机化学与普通化学杂志》1995,621(11):1844-1848
Further investigation of the reaction of Ar*GaCl2 (Ar* = 2,4,6-t-Bu3C6H2) with Na[Mn(CO)5] resulted in the new compound, [Ga(Ar*){Mn(CO)5}2] 2 . The new indium compounds, [In(Ar*){Co(CO)4}2] 3 and [In(Ar*){Mn(CO)5}2] 4 , have been prepared by the treatment of Ar*InBr2 with Na[Co(CO)4] and Na[Mn(CO)5], respectively. The structure of 3 was established by single-crystal X-ray diffraction: space group P1 (No. 2), Z = 2, a = 8.625(1) Å, b = 10.557(2) Å, c = 17.55(2) Å, α = 88.43(1)°, β = 83.45(1)°, γ = 71.14(1)°. The X-ray crystal structure of [Ga{Mn(CO)5}3] is also reported: space group Pbca (No. 61), Z = 8, a = 12.83(3) Å, b = 11.753(2) Å, c = 29.662(6) Å, α = β = γ = 90°. 相似文献
16.
Synthesis and Spectroscopic Characterization of [Rh(SeCN)6]3– and trans ‐[Rh(CN)2(SeCN)4]3–, Crystal Structure of (Me4N)3[Rh(SeCN)6] Treatment of RhCl3 with KSeCN in acetone yields a mixture of selenocyanato‐rhodates(III), from which [Rh(SeCN)6]3– and trans‐[Rh(CN)2(SeCN)4]3– have been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X‐ray structure determination on a single crystal of (Me4N)3[Rh(SeCN)6] (trigonal, space group R3, a = 14.997(2), c = 24.437(3) Å, Z = 6) reveals, that the compound crystallizes isotypically to (Me4N)3[Ir(SCN)6]. The exclusively via Se coordinated selenocyanato ligands are bonded with the average Rh–Se distance of 2.490 Å and the Rh–Se–C angle of 104.6°. In the low temperature IR and Raman spectra the metal ligand stretching modes ν(RhSe) of (n‐Bu4N)3[Rh(SeCN)6] ( 1 ) and trans‐(n‐Bu4N)3[Rh(CN)2(SeCN)4] ( 2 ) are in the range of 170–250 cm–1. In 2 νas(CRhC) is observed at 479 cm–1. The vibrational spectra are assigned by normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are fd(RhSe) = 1.08 ( 1 ), 1.10 ( 2 ) and fd(RhC) = 3.14 mdyn/Å ( 2 ). fd(RhS) = 1.32 mdyn/Å is determined for [Rh(SCN)6]3–, which has not been calculated so far. The 103Rh NMR resonances are 2287 ( 1 ), 1680 ppm ( 2 ) and the 77Se NMR resonances are –32.7 ( 1 ) and –110.7 ppm ( 2 ). The Rh–C bonding of the cyano ligand in 2 is confirmed by a dublett in the 13C NMR spectrum at 136.3 ppm. 相似文献
17.
Tetranuclear Cluster Complexes of the Type [MM′(AuR3)2(μ‐H)(μ‐PCy2)(μ4‐PCy)(CO)6] (M,M′ = Mn, Re; R = Ph, Cy, Et): Synthesis, Structure, and Topomerisation The dirhenium complex [Re2(μ‐H)(μ‐PCy2)(CO)7(ax‐H2PCy)] ( 1 ) reacts at room temperature in thf solution with each two equivalents of the base DBU and of ClAuPR3 (R = Ph, Cy, Et) in a photochemical reaction process to afford the tetranuclear clusters [Re2(AuPR3)2(μ‐H)(μ‐PCy2)(μ4‐PCy)(CO)6] (R = Ph ( 2 ), Cy ( 3 ), Et ( 4 )) in yields of 35–48%. The homologue [Mn2(μ‐H)(μ‐PCy2)(CO)7(ax‐H2PCy)] ( 5 ) leads under the same reaction conditions to the corresponding products [Mn2(AuPR3)2(μ‐H)(μ‐PCy2)(μ4‐PCy)(CO)6] (R = Ph ( 6 ), Et ( 8 )). Also [MnRe(μ‐H)(μ‐PCy2)(CO)7(ax/eq‐H2PCy)] ( 9 ) reacts under formation of [MnRe(AuPR3)2(μ‐H)(μ‐PCy2)(μ4‐PCy)(CO)6] (R = Ph ( 10 ), Et ( 11 )). All new cluster complexes were identified by means of 1H‐NMR, 31P‐NMR and ν(CO)‐IR spectroscopic measurements. 2 , 4 and 10 have also been characterized by single crystal X‐ray structure analyses with crystal parameters: 2 triclinic, space group P 1, a = 12.256(4) Å, b = 12.326(4) Å, c = 24.200(6) Å, α = 83.77(2)°, β = 78.43(2)°, γ = 68.76(2)°, Z = 2; 4 monoclinic, space group C2/c, a = 12.851(3) Å, b = 18.369(3) Å, c = 40.966(8) Å, β = 94.22(1)°, Z = 8; 10 triclinic, space group P 1, a = 12.083(1) Å, b = 12.185(2) Å, c = 24.017(6) Å, α = 83.49(29)°, β = 78.54(2)°, γ = 69.15(2)°, Z = 2. The trapezoid arrangement of the metal atoms in 2 and 4 show in the solid structure trans‐positioned an open and a closed Re…Au edge. In solution these edges are equivalent and, on the 31P NMR time scale, represent two fluxional Re–Au bonds in the course of a topomerization process. Corresponding dynamic properties were observed for the dimanganese compounds 6 and 8 but not for the related MnRe clusters 10 and 11 . 2 and 4 are the first examples of cluster compounds with a permanent Re–Au bond valence isomerization. 相似文献
18.
Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of the Linkage Isomeric Chlororhodanoiridates(III) trans-[IrCl2(SCN)4]3? and trans-[IrCl2(NCS)(SCN)3]3? By treatment of Na2[IrCl6] with NaSCN in 2N HCl the linkage isomers trans-[IrCl2(SCN)4]3? and trans-[IrCl2(NCS)(SCN)3]3? are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. X-ray structure determinations on single crystals of trans-(n-Bu4N)3[IrCl2(SCN)4] ( 1 ) (monoclinic, space group P21/a, a = 18.009(4), b = 15.176(3), c = 23.451(4) Å, β = 93.97(2)°, Z = 4) and trans-(Me4N)3[IrCl2(NCS)(SCN)3] ( 2 ) (monoclinic, space group P21/a, a = 17.146(5), b = 9.583(5), c = 18.516(5) Å, β = 109.227(5)°, Z = 4) reveal the complete ordering of the complex anions. The via S or N coordinated thiocyanate groups are bonded with Ir? S? C angles of 105.7–109.7° and the Ir? N? C angle of 171.4°. The torsion angles Cl? Ir? S? C and N? Ir? S? C are 3.6–53.0°. The IR and Raman spectra of ( 1 ) are assigned by normal coordinate analysis using the molecular parameters of the X-ray determination. The valence force constants are fd(IrS) = 1.52 and fd(IrCl) = 1.72 mdyn/Å. 相似文献
19.
The syntheses of homo‐ and heteropentanuclear coordination compounds with the molecular formulae [MZn4(L)4(L′)6] (M = CoII or Zn; L = chloride or acac; L′ = 1,2,3‐benzotriazolate) are reported. These compounds display a highly symmetric coordination unit consisting of a central metal ion (M = CoII or Zn) which is octahedrally coordinated by 6 tridentate benzotriazolate‐type ligands via their N(2) donor atom. The benzotriazolate ligands span the edges of an imaginary tetrahedron thus providing four coordination sites at the corners of the tetrahedron, which are then filled by four zinc ions. The coordination shell of the latter are completed by bidentate acetylacetonate (acac) ligands or by chloride anions, respectively. The solid state structures of two homopentanuclear metal complexes, namely [Zn5(acac)4(bta)6]·4C6H12 ( 1 ) (acacH = acetylacetone; btaH = 1,2,3‐benzotriazole), and [Zn5Cl4(Me2bta)6]·2DMF ( 2 ) (Me2btaH = 5,6‐dimethyl‐1,2,3‐benzotriazole) were determined by single crystal X‐ray structure analysis. The heteropentanuclear metal complex [CoIIZn4Cl4(Me2bta)6]·2DMF ( 3 ) is isostructural with compound 2 . Compound 1 was synthesized from stoichiometric amounts of Zn(acac)2 and btaH employing dichloromethane as solvent. The synthesis of compound 2 requires addition of an auxiliary base to the DMF solution of anhydrous ZnCl2 and Me2btaH. For compound 3 a stoichiometric ratio of Co(NO3)2·6H2O, anhydrous ZnCl2 and Me2btaH was employed during synthesis. Phase purity of all compounds was proved by X‐ray powder diffraction (XRPD) analysis, IR spectroscopy, and elemental analysis. Crystal data: for 1 (C80H100N18O8Zn5): monoclinic, space group P21/c with a = 23.781(5) Å, b = 16.000(3) Å, c = 25.170(5) Å, β = 115.29(3)°, V = 8659(3) Å3, Z = 4, ρ = 1.357 g cm?3. For 2 (C54H62Cl4N20O2Zn5): cubic, space group with a = 23.367(3) Å, V = 12759(3) Å3, Z = 8, ρ = 1.553 g cm?3. For 3 (C54H62Cl4CoN20O2Zn4): cubic, space group with a = 23.443(3) Å, V = 12884(3) Å3, Z = 8, ρ = 1.532 g cm?3. 相似文献
20.
The Crystal Structures of [Cu2Cl2(AA · H+)2](NO3)2 and [AA · H+]Picr? (AA · H+ = Allylammonium; Picr? = Picrat) By an alternating current electro synthesis the crystal-line π-complex [Cu2Cl2(AA · H+)2](NO3)2 has been obtained from CuCl2 · 2H2O, allylamine (AA), and HNO3 in ethanolic solution. X-ray structure analysis revealed that the compound crystallized in the monoclinic system, space group P21/a, a = 7.229(3), b = 7.824(3), c = 26.098(6) Å, γ = 94.46(5)°, Z = 4, R = 0.025 for 2 023 reflections. The crystal structure is built up of CunCln chains which are connected by π-bonding bidentate AA · H+ …? ON(O)O …? H+ · AA units. For comparision with the above complex the structure of [AA · H+]Picr? (Picr? = picrate anion) is also reported. 相似文献