共查询到20条相似文献,搜索用时 15 毫秒
1.
Alternative Ligands. XXII. Rhodium(I) complexes with Donor/Acceptor Ligands of the Typs Me2PCH2CH2SiXnMe3?n(X = F, Cl, OMe) Donor/acceptor ligand of the type Me2PCH2SiXnMe3?n react with [Rh(CO)2Cl]2 ( 1 ) to give the mononuclear complexes RhCl(CO)(PMe2CH2CH2SiXnMe3?n)2 ( 2-6 , Table 1) with planar geometry of the donor atoms, one exception being Me2PCH2CH2CH2SiCl3, yielding the crystalline RhIII-complex RhCl2(CO)(PMe2CH2CH2SiCl2)(PMe2CH2CH2SiCl3) ( 7 ) by oxidative addition of one of the SiCl bonds to the Rh1 precursor. Structures with Rh → Si interaction between the basic central atoms and the acceptor group SiXnMe3?n could be detected in the isolated products neither spectroscopically nor by X-ray diffraction of the two representatives RhCl(CO)(PMe2CH2CH2SiF3)2 ( 2 ) and RhCl(CO)[PMe2CH2CH2siF3]2 ( 2 ) and RhCl(CO) [PMe2CH2CH2Si(OMe3]2 ( 6 ). The presence of such acid/base adducts in the reaction mixture is indicated for the more acidic acceptor groups SiXnMe3?n byvco values near 1990cm?1, (see Table 3). The complex RhCl(CO)PMe3)(PMe2CH2CH2SiF3 ( 8 ) is obtained by the reaction of RhCl(CO)(PMe3)2 ( 9 ) with Me2PCH2SiF3 and has been identified spectroscopically in a mixture with 2 and 9 . 相似文献
2.
Alternative Ligands. XXIV. Rhodium(I) Complexes with P-Donor and Sn- or B-Acceptor Ligands Donor/acceptor ligands of the type Me2PCH2CH2SnMe3 (1) , (Me2PCH2CH2)2SnMe2 (2) , and Me2PCMe=CMeBMe2 (3) , respectively, have been prepared by hydrostannlation of Me2PVi with Me3SnH or Me2SnH2 and by a multistep synthesis via Na[Me3BH], Na[Me3BC?;CMe] using Me2PCI as partner, respectively. The new ligands were used to produce the Rh(I) complexes RhCI(CO)(Me2PCH2CH2SnMe3)2 (5) , RhCI(CO)(Me2PCH2CH2)2SnMe2 (7), and RhCI(CO)(Me2PCMe=CMeBMe2)2 (8) by reactions of Rh(CO)2CH2 (4) with the corresponding ligands. In addition, the VASKA type compounds RhCI(CO)(Me2PVi)2 (6) and RhCI(CO)(PMe3)2 were prepared in order to test an alternative route to 5 or to from the known adduct RhCI(CO)(PMe3)2. BBr3 (9) . RhBr(CO)(PMe3)2 (10) and the binuclear system [RhBr(CO)PMe3]2 (11) were identified spectroscopically after working up the 1:1 reaction mixture of RhCI(CO)(PMe3)2 and BBr3. Reasonable pathways are suggested for their formation. ?Metallbase”?/acceptor interaction show up, on the one hand, in following reactions in case of the ligands with Sn acceptors, on the other hand, in significant changes of spectroscopic data for 8 . New compounds of sufficient stability were characterized by analytical (C, H) and spectroscopic (MS, IR. NMR) investigations. 相似文献
3.
Alternative Ligands. XXI. Novel Donor/Acceptor Ligands Me2PCH2CH2SiFnMe3-n, Me2PCH2CH2SiR(C6H4F)2, and (2-Me2PC6H4)SiXMe2 Donor/acceptor ligands of the type Me2PCH2CH2SiX3 [X = Cl ( 1 ), F ( 2 ), Me ( 3 ), OMe ( 4 )], (Me2PCH2CH2)2SiX2 [X = Cl ( 6 ), F ( 7 )], Me2PCH2CH2SiX(C6H4F)2 [X = F ( 5 ), Me ( 8 )], and Me2PCH2CH2SiXnMe3-n[n = 1; X = Cl ( 10 ), F ( 11 ); n = 2; X = F ( 9 )] are prepared in yields between 42 and 95% by photochemical addition of Me2PH to the corresponding vinylsilane precursors. In case of the halogen containing representatives formation of solid polyadducts, due to Lewis acid/base interaction between P-donor and Si-acceptor function, reduces the yields. Ligands of the type (2-Me2PC6H4)SiXMe2 [X = NMe2 ( 12 ), Cl ( 13 ), F ( 14 )] are obtained by two different routes (Abb. 3), using 2-chlorobromobenzene as the starting material. New compounds have been characterized by analytical (C, H) and spectroscopic (NMR, MS) investigations. In order to elucidate the associative properties compounds 2 and 9 were used for the following experiments:
- – Study of the influence of dissolution on the proton and fluorine resonances of 2 and 9 ,
- – investigation of the adduct equilibrium (–H2CF3Si←PMe2CH2–)n + nBF3 → n[F3B←PMe2CH2CH2SiF3],
- – cleavage of the polyadduct of 2 using [NH4]F and [Me4N]F, respectively, for the formation of hexacoordinate complex anions [Me2PCH2CH2SiF5]2?.
4.
Alternative Ligands. XVII. Reaction of the Lewis Base [Mn(CO)5]? with Donor/Acceptor Ligands Me2PCH2CH2SiX3 (X = Cl, F, OMe) Reactions [eqn. (1) and (2)] for the preparation of intramolecular adducts between the base [Mn(CO)4PMe2R]? and the Lewis acidic terminal group SiX3 of the ligands Me2PCH2CH2SiX3 (X = Cl, F, OMe) have been studied. Cleavage of the MnSi bond with Cl? [equ.(2)] in the chelate complex to form the complex salt [Ph4As][Mn(CO)4PMe2 CH2CH2SiCl3] proves unsuccessful because of the surprising stability of this bond. The alternative route [equ. (1)] yields the anionic species [Mn(CO)4PMe2CH2CH2SiX3]? in the first step, but reaction conditions favour the formation of with decreasing tendency Cl> F> OMe. The complex salts, therefore, cannot be isolated as pure compounds. 相似文献
5.
Joseph Grobe Elke Maria Reifer Bernt Krebs Mechtild Lge Markus Prill 《无机化学与普通化学杂志》2000,626(2):478-488
Alternative Ligands. XXXV. Syntheses of Bidentate P‐Donor/Sn‐Acceptor Ligands: Coordination Experiments with Cp*Rh(CO)2 and CpRh(C2H4)2 Donor/acceptor ligands Me2Sn(CH2CH2PMe2)2 ( 1 ) and Me2Sn(OCH2PMe2)2 ( 2 ) have been prepared by radical reaction of Me2PVi with Me2SnH2 and by substitution of chlorine in Me2SnCl2 or of ethoxy groups in Me2Sn(OEt)2 by MOCH2PMe2 (M = Li, Na) and HOCH2PMe2, respectively. 2 cannot be isolated in pure form from the product mixture because, due to condensation reactions, the “ladder structure” [Me2Sn(OCH2PMe2)2OSnMe2]2 ( 3 ) is formed. The molecular structure of 3 was determined by X‐ray diffraction studies of single crystals. Attempts to produce the thiophosphoryl derivative of 3 result in the degradation of the ladder structure giving the thermally labile phosphane sulfide Me2Sn(OCH2P(S)Me2)2. Ligands 1 and 2 besides Me2PCH2CH2SnMe3 ( 4 ) have been used for the preparation of rhodium(I) complexes from Cp*Rh(CO)2 ( 5 ) or CpRh(C2H4)2 ( 10 ) as educts. The thermal reaction of 5 with 4 yields Cp*Rh(CO)PMe2CH2CH2SnMe3 ( 6 ), that of 5 with 1 a mixture of the mononuclear derivative Cp*Rh(CO) · PMe2CH2CH2SnMe2CH2CH2PMe2 ( 7 ) and the binuclear complex [Cp*Rh(CO)PMe2CH2CH2]2SnMe2 ( 8 ). The related system [Cp*Rh(CO)PMe2CH2O]2SnMe2 produced by reaction of 5 with 2 can only be detected in solution but, because of some side‐products, was not fully characterized. From 10 and 4 a mixture of mono‐ and disubstituted products, CpRh(C2H4)PMe2CH2CH2SnMe3 ( 11 ) and CpRh(PMe2CH2CH2SnMe3)2 ( 12 ), is obtained. Reaction of 1 with 10 yields a mixture of the complexes CpRh(C2H4)PMe2CH2CH2SnMe2CH2CH2PMe2 ( 13 ) and CpRh(Me2CH2CH2)2SnMe2 ( 14 ). Some of the NMR data (13C, δδSn) of 14 can be interpreted in terms of the expected Rh → Sn interaction. A definite proof by X‐ray diffraction on single crystals, so far, was not possible. 相似文献
6.
Preparation and Catalytic Properties of Rhodium(I) Complex Salts of the Type [Rh(COD)(o-Py(CH2)2 P(Ph)(CH2)3ZR)]PF6 (Z = O, NH) . In dichloromethane solutions were reacted [Rh(COD)Cl]2 (COD = cis,cis-1.5-cyclooctadiene) with each of the four new ligands of the type o-Py(CH2)2P(Ph)(CH2)3ZR in the presence of the halogen scavenger TIPF6 at 0°C to complex salts [Rh(COD) (o-Py(CH2)2P(Ph)(CH2)3ZR]PF6 (ZR = OC2H5, I ; OPh, II ; NHPh, III ; NHcyclo? C6H11, IV ). The Rh1 complex cation in the obtained compounds I – IV coordinates besides the bedentate COD group the ligand donor atoms P und pyridinic N and the remaining donor atom Z is uncoodinated in an assumed square planar ligand geometry at the Rh central atom. In 1.4 dioxane solutions the complex catalysts I – IV polymerize at 25°C the substrate phenylacetylene (PA) to polyphenylacetylene (PPA): values of TON [h?1] between 352 ( I ) and 876 ( IV ), and average molecular weights Mw (GPC measurements) between 238 000 ( I ) and 199 900 ( IV ). These given values exhibit a dependency on the ZR group in complexes I – IV . The microstructure of isolated PPA is cis-transoidal. It is formed stereospezific and, based on MNDO calculations, is thermodynamically favoured. For the purpose of comparison, from both the newly synthesized compounds of the type [Rh(COD)DBN- (or DBU)Cl] (DBN = 1.5-Diazabi-cyclo[4.3.0.]non-5-en, DBU = 1.8-Diazabicycl0[5.4.0]- undec-7-en) was obtained a larger value of TON with 1292 (or 1327) [h?], but a lower value of M, with 166200 (or 131200). These catalysts including I –IV polymerize PA to PPA at a lower reaction temperature with improved selectivity and larger values of Mw as hitherto known catalyst systems. 相似文献
7.
Alternative Ligands. XXV. New Chelating Ligands of the Type Me2ESiMe2(CH2)2E′Me2 (E=P, As; E′=N, P, As) Chelating ligands of the type Me2EsiMe2(CH2)2E′ Me2, have been prepared by the following routes: Starting from Me2Si(Vi)Cl, the compounds with E=N and E′ =N ( 1 ), P ( 2 ), As ( 3 ) are obtained in yields of 65 to 78% by aminolysis to yield Me2NSiMe2Vi, followed by the LiE′ Me2 catalyzed addition of He′Me2 to the vinyl group. The intermediates ClSiMe2(CH2)E′Me2 [E′=N ( 4 ), P ( 5 ), As ( 6 )] are produced by the reactions of 1 to 3 with PhPCl2. 5 and 6 can be prepared in a purer form by the photochemical addition of HPMe2 and HAsMe2, respectively, to the vinyl group of Me2Si(Vo)Cl. 4 to 6 react with LiEMe2, in situ prepared from n-BuLi and HEMe2, to yield the ligands Me2ESiMe2(CH2)2E′Me2 ( 7–12 ) (E=P, As; E′=N, P, As). The new compounds have been characterized by analytical and spectroscopic investigations (NMR, MS). 相似文献
8.
Wiktor I. Owtscharenko Erhard Schnell Karl-E. Schwarzhans 《Monatshefte für Chemie / Chemical Monthly》1987,118(6-7):773-777
A series of complexes formed between the copper(II) metal ion and the semicarbazone of the stable free radical 2-acetyl-2,5,5-trimethyl-4-phenyl-3-imidazoline-3-oxid-1-oxyl and the analogous hydroxylamine has been prepared. By analysis of the IR spectra of the complexes the coordination mode of the ligands was determined. 相似文献
9.
Preparation of Chelating Ligands of the Type Me2XSiMe2CH2X′Me2 (Me = CH3; X, X′ = N, P and/or As) Chelating Ligands of the general type Me2XSiMe2CH2X′Me2 (Me = CH3; X, X′ = N, P As) are obtained from ClSiMe2CH2Cl by the following reactions (see “Inhaltsübersicht”). The new compounds have been characterized by analytical and spectroscopic methods (IR, NMR, MS). 相似文献
10.
Neutral and Cationic Ruthenium(II) Complexes with Trifunctional Phosphane Ligands Compounds of the type [RuCl2(RPX2)2] 4 – 7 (R = iPr, tBu; X = CH2CH2OMe, CH2CO2Me) were prepared by reacting RPX2 with either RuCl3 · 3H2O or [RuCl2(PPh3)3], respectively. In 4 – 7 the trifunctional phosphanes coordinate as bidentate ligands to the metal center through the phosphorus atom and the oxygen atom of a methoxy or carbonyl group. The lability of the Ru–O bond allows substitution reactions with CO, tert-butylisonitrile and phenylacetylene. The Ru–Cl bonds in 5 (R = tBu; X = CH2CH2OMe) can be cleaved upon treatment with one or two equiv of AgPF6 yielding mono- or dicationic derivatives. In these complexes the ligands are coordinated to the metal center through the phosphorus and both of the oxygen donor atoms. The reaction of the phosphinoesterenolate compound 17 with Ph2C=C=O leads to the insertion of two molecules of the ketene into the C–H bond of one of the five-membered metal-enolate rings to yield the “expanded” chelate complex 18 , the structure of which was determined by X-ray crystallography. 相似文献
11.
Chemistry of Polyfunctional Molecules. 124. Silver(I) Complexes Containing the Ligands Bis(diphenylphosphanyl)amine, -amide and Tris(diphenylphosphanyl)amine Bis(diphenylphosphanyl)amine HN(PPh2)2 ( 1 ) reacts with AgCl to the complex HN(PPh2AgCl)2 ( 5 ) for which in the solid state the cluster structure Ag4Cl4[HN(PPh2)2]2 is assumed. Reaction of 5 with LiN(PPh2)2 ( 2 ) gives the known [N(PPh2AgPh2P)2N] ( 8 ) and the new complex [Ag(μ—Ph2PNPPh2)2(μ—Ph2PNHPPh2)Ag] · dioxane ( 7 · dioxane). The compound 7 · dioxane has been characterized by X-ray diffraction. The molecules are found to contain a bicyclo[3.3.3]undecane-type structure with trigonal planar coordinated silver atoms, which are separated by 281,6(1) pm. The dioxane is bound via H-bridge bond to the NH group of the coordinated HN(PPh2)2. Treatment of 8 with ClPPh2 yields N(PPh2AgCl)3 ( 12 ), which has also been obtained by the reaction of N(PPh2)3 ( 3 ) with silver chloride. All the compounds have been characterized, so far as possible, by IR, Raman, 1H NMR, 31P{1H} NMR, 13C{1H} NMR and mass spectroscopy. 相似文献
12.
Roland Lang Arno Schrwerth Kurt Polborn Walter Ponikwar Wolfgang Beck Theodor Severin Kay Severin 《无机化学与普通化学杂志》1999,625(8):1384-1390
Organometallic Compounds with N -substituted 3-Hydroxy-2-methyl-4-pyridone Ligands: square planar Rhodium(I), Iridium(I), and Palladium(II) Complexes Reactions of [(OC)2MCl]2 (M = Rh, Ir) or [(cod)RhCl]2 with the anions of N-Aryl or N-Alkyl substituted 3-hydroxy-2-methyl-4-pyridones (O–O′) yield complexes of the general formula [L2M(O–O′)]. Compounds of this type are also available from reactions of [(OC)2Rh(acac)] with the corresponding neutral ligands. Substitution of one carbonyl-ligand of the N-phenyl complex [(OC)2Rh(C12H10NO2)] ( 2 ) with cyclooctene affords [(OC)(C8H14)Rh(C12H10NO2)] ( 8 ). The palladium complexes [(R3P)Pd(O–O′)Cl] (R = Et, Bu), [(C6H4CH2NMe2) · Pd(O–O′)] and [(Et3P)2Pd(O–O′)]BF4 ( 9 – 12 ) were synthesized from [(R3P)PdCl2]2, [(C6H4CH2NMe2)PdCl]2 or [(Et3P)PdCl2]. The structures of the N-methyl compounds [(OC)2Rh(C7H8NO2)] ( 1 ) and [(Ph3P)Pd(C7H8NO2)Cl] ( 9 ) were determined by single crystal X-ray diffraction. 相似文献
13.
M. Leschke H. Lang M. Melter G. Rheinwald C. Weber H. A. Mayer H. Pritzkow L. Zsolnai A. Driess G. Huttner 《无机化学与普通化学杂志》2002,628(2):349-356
The title compounds 3‐5 are accessible by treatment of P(C6H4CH2NMe2)3( 1 ) with CuX ( 2a : X = Cl, 2b : X = Br, 2c : X = I) in the ratio of 1:1 or 1:2 in very good yields. Reaction of 1 with equimolar amounts of 2a affords the copper(I) chloride [P(C6H4CH2NMe2)3]CuCl ( 3 ). With a further equivalent of 2a homobimetallic [P(C6H4CH2NMe2)3]Cu2Cl2 ( 4 ) is formed, which also can be synthesized by the reaction of 1 with two equivalents of 2a. Complex 3 reacts with CuX (X = Br, I)to afford [P(C6H4CH2NMe2)3]Cu2ClX ( 5a : X = Br; 5b : X = I) in which mixed halides are present. The newly synthesized complexes 3‐5 were characterized by elemental analyses, by their IR‐, 1H‐, 13C{1H}‐ and 31P{1H}‐NMR spectra as well as by mass spectrometrical studies. The solid‐state structures of complexes 3 and 4 are reported. Mononuclear 3 crystallizes in the monoclinic space group P21/c with the cell parameters a = 14.285(2), b = 10.853(2), c = 17.425(2) Å , β = 103.310(10)?, V = 2628.9(7) Å 3 and Z = 4 with 4053 observed unique reflections; R1 = 0.0314. The crystal structure of 3 consists of monomeric molecules with planar coordinated copper(I) centres (CuClNP). Homobimetallic 4 crystallizes in the monoclinic space group P21/n with a = 23.905(4), b = 10.874(3), c = 25.314(5), β = 99.130(10)?, V = 6497(2) /Aring; 3 and Z = 4 with 9021 observed unique reflections; R1 = 0.0480. In 4 one of two copper(I) centres possesses a distorted trigonal‐pyramidal environment, while the other one is almost square‐pyramidal coordinated. The Cu2Cl2 segment resembles to a building block which is set up by a contact ion pair consisting of Cu+ and [CuCl2]‐ , respectively. 相似文献
14.
Ingrid Bartz Joseph Grobe Kai Lütke‐Brochtrup Bernt Krebs Joachim Kuchinke Mechtild Lge 《无机化学与普通化学杂志》2001,627(6):1334-1346
Alternative Ligands. XXXVI. Novel Rhodium(I) Complexes with Donor/Acceptor Chelating Ligands In order to generate metal base/Lewis‐acid interactions in rhodium(I) phosphane complexes the binuclear complex [Rh(CO)2Cl]2 was reacted in benzene with dipod ligands of the type R2M′(OCH2PMe2)x(CH2CH2PMe2)2–x (R = F, Me; M′ = Si, Ge; x = 0–2) using the Ziegler dilution principle with the aim to produce mononuclear compounds in which with formation of five‐membered chelate rings in principle Rh → M′ contacts are possible. The reactions of ligands 1 – 7 (Table 1) with [Rh(CO)2Cl]2 proceed under CO elimination and, in spite of large turnovers, lead to a variety of products 8 – 14 (Table 1), in case of 11 , 13 and 14 accompanied by degradation of the corresponding ligands. Intact ligands are present in the 16‐membered rings of the binuclear complexes 8 – 10 and 12 , for which, due to the molecular structure, Rh → M′ interactions can be excluded. In the reaction of Me2Si(OCH2PMe2)2 ( 4 ) with [Rh(CO)2Cl]2 the unusual binuclear system 11 with a central Rh2O2 four‐membered ring and two RhO(SiMe2OCH2PMe2) six‐membered rings is formed. Small amounts of the mononuclear compounds Rh(CO)Cl(Me2PCH2OH)2 ( 13 ) and Rh(CO)Cl3(Me2PCH2OH)2 ( 14 ), respectively, are obtained in crystalline form from the reaction mixtures of [Rh(CO)2Cl]2 with Me2Ge(OCH2PMe2)(CH2CH2PMe2) ( 6 ) or Me2Ge(OCH2PMe2)2 ( 7 ). The new complexes were characterized by analytic (C, H), spectroscopic (NMR, IR, MS) and, except for 12 , by single crystal structural analyses. 相似文献
15.
Synthesis and Structure of Cobalt(III) Complexes of 14-Membered cis- and trans-N2S2 Dibenzo Macrocycles with two Pendant Acetato Groups The isomeric fourteen membered macrocyclic ligands 6,7,9,15,16,18-hexahydrodibenzo[f,m][1,8]dithia[4,11]diazacyclotetradecine-8,17-diacetic acid-0.5-hydrate (H2L3), C22H26N2O4S2 · 0.5 H2O and 6,7,13,15,16,18-hexahydrodibenzo-[e,m][1,4]dithia[8,11]diazacyclotetradecine-14,17-diacetic acid-1.5-hydrate (H2L6), C22H26N2O4S2 · 1.5 H2O with cis- and trans-N2S2 donorsets and two pendant acetato groups form the stable complexes [Co(L3)]ClO4 · 2 H2O ( 1 ) and [Co(L6)]ClO4 · H2O ( 2 ). Co(III) is octahedrally coordinated herein to all six donor centers of the respective ligand. The macrocyclic rings are folded. The metal ions are located outside the macrocyclic cavity. The mean Co? N, Co? O and Co? S distances are 196, 190 and 224 pm, respectively. Crystal data: 1 , monoclinic, space group C2/c, a = 3 797.7(9), b = 763.8(3), c = 2 207.0(7) pm, β = 123.17(2), Z = 8, 3 445 reflections, R(Rw) = 0.072(0.070); 2 , monoclinic, space group C2/c, a = 3 197.1(6), b = 880.4(2), c = 1 890.6(4) pm, β = 112,19(3)°, Z = 8, 4 415 reflections, R(Rw) = 0.062(0.064). 相似文献
16.
Preparation of Trifluormethylhalogen Iodate(I) Salts (CH3)4N+CF3IX? (X = F, Cl, Br) and Trifluormethyltrifluormethoxy Iodate(I) (CH3)4N+CF3IOCF3? We describe the preparation of new trifluormethyliodate(I) salts CF3IX? (X = F, Cl, Br, OCF3). (CH3)4N+CF3ICl? and (CH3)4N+CF3IBr? are obtained via addition of CF3I with the corresponded tetramethylammonium halogenide. (CH3)4N+CF3IOCF3? is synthesized by comproportionation of (CH3)4N+CF3ICl? with CF3OCl under formation of Cl2 at ?78°C. (CH3)4N+CF3IF? is formed either, through thermolysis of (CH3)4N+ CF3IOCF3? under separation of COF2, or reaction of CF3I with (CH3)4N+ OCF3?. The thermolabile compounds have been characterized by i.r., Raman, 19F-, 13C NMR spectroscopy. 相似文献
17.
Chelate Complexes of the Type M(CO)4(Me2XGeMe2CH2X′Me2) (M) = Cr, Mo, W; X, X′ = N, P, As; Me = CH3) The ligands (Me2)XGeMe2CH2X′Me2 (M) = Cr, Mo, W) react with M(CO)4norbor (norbor = Norbornadiene) (M = Cr, Mo, W) yielding the chelate complexes M(CO)4(Me)2XGeMe2CH2X′Me2). compounds of low thermal stability are formed with the ligands (Me2NGeMe2CH2X′Me2 because of the weak donor ability of the GeNMe2 group and with Me2AsGeMe2CH2NMe2 caused by strong steric ring tension. The new compounds are characterized by analytical and spectroscopic (n.m.r., i.r., m.s.) investigations. 相似文献
18.
Open sheet and framework structures [CuX{cyclo-(MeAsO)4}] (X=Cl, Br, I) 1 – 3 and [Cu3X3{cyclo-(MeAsO)4}2] (X=Cl, Br) 4 and 5 may be prepared by self-assembly from CuX and methylcycloarsoxane (MeAsO)n in acetonitrile solution. 1 – 3 exhibit 44 nets in which (CuX)2 units are connected through μ-1 KAs1 : 2 KAs3 coordinated (MeAsO)4 ligands into large 28-membered rings. In contrast, adjacent [CuX] chains in 4 and 5 are connected into sheets by μ4-K4 As coordinated (MeAsO)4 building blocks, with μ-1 KAs1 : 2 KAs3 bridging of these layers by independent (MeAsO)4 cyclotetramers leading to the generation of a porous framework structure. 1 – 5 were characterised by X-ray structural analysis. 相似文献
19.
Synthesis of Copper and Silver Complexes with Pentadentate N,S and Hexadentate N,O Chelate Ligands – Characterization and Crystal Structures of {Cu2[C6H4(SO2)NC(O)]2(C5H5N)4}, {Cu2[C5H3N(CHNC6H4SCH3)2]2}(PF6)2, and {Ag[C5H3N(CHNC6H4SCH3)2]}PO2F2 In the course of the reaction of copper(II)-acetate monohydrate with 2,2′-bisbenzo[d][1,3]thiazolidyl in methanol the organic component is transformed to N,N′-bis-(2-thiophenyl)ethanediimine and subsequently oxidized to the N,N′-bis-(2-benzenesulfonyl)ethanediaciddiamide H4BBSED, which coordinates in its deprotonated form two Cu2+ ions. Crystallisation from pyridine/n-hexane yields [Cu2(BBSED)(py)4] · MeOH. It forms triclinic crystals with the space group P1 and a = 995.5(2) pm, b = 1076.1(3) pm, c = 1120.7(2) pm, α = 104.17(1)°, β = 105.28(1)°, γ = 113.10(1)° and Z = 1. In the centrosymmetrical dinuclear complex the copper ions are coordinated in a square-pyramidal arrangement by three nitrogen and two oxygen atoms. The Jahn-Teller effect causes an elongation of the axial bond by approximately 30 pm. The reactions of the pentadentate ligand 2,6-Bis-[(2- methylthiophenyl)-2-azaethenyl]pyridine BMTEP with salts of copper(I), copper(II) and silver(I) yield the complexes [CU2(BMTEP)2](PF6)2, [Cu(BMTEP)]X2 (X = BF, C1O) and [Ag(BMTEP)]X (X = PO2F, ClO). [Cu2(BMTEP)2](PF6)2 crystallizes from acetone/diisopropyl- ether in form of monoclinic crystals with the space group C2/c, and a = 1833.2(3) pm, b = 2267.30(14) pm, c = 1323.5(2) pm, β= 118.286(5)°, and 2 = 4. In the dinuclear complex cation with the symmetry C2 the copper ions are tetrahedrally coordinated by two bridging BMTEP ligands. The Cu? Cu distance of 278.3pm can be interpreted with weak Cu? Cu interactions which also manifest itself in a temperature independent paramagnetism of 0.45 B.M. The monomeric silver complex [Ag(BMTEP)]PO2F2 crystallizes from acetone/thf in the triclinic space group P1 with a = 768.7(3) pm, b = 1074.0(5) pm, c = 1356.8(5) pm, α = 99.52(2)°, β = 96.83(2)°, γ = 99.83(2)° and Z = 2. The central silver ion is coordinated by one sulfur and three nitrogen atoms of the ligand in a planar, semicircular arrangement. The bond lengths Ag? N = 240.4–261.7 and Ag? S = 257.2 pm are significantly elongated in comparison with single bonds. 相似文献
20.
Triphenylphosphane Nickel(0) Complexes with Isocyanide Ligands — [(RNC)nNi(PPh3)4–n] (n = 1–3) Synthesis and properties of the isocyanide triphenylphosphane nickel(0) complexes [(RNC)Ni(PPh3)3], [(RNC)2Ni(PPh3)2] and [(RNC)3Ni(PPh3)] (R = tBu, Cy, PhCH2, p-TosCH2) are described. I.r. and 31P n.m.r. spectra were recorded and the X-ray crystal structure of [(PhCH2NC)2Ni(PPh3)2] was determined. 相似文献