Synthesis and Spectroscopic Characterisation of some Pentacarbonyltungsten(0) Complexes with Mono‐ and Bicyclic Phosphirane Ligands: Crystal Structure of [{(Me3Si)2HCPC(H)H–C(H)Ph}W(CO)5] The tungsten(0) complex [{(Me3Si)2HCPC(Ph)=N}W(CO)5] ( 1 ) reacts upon heating with alkene derivatives 2 , 6 , 8 , and 10 in toluene to form benzonitrile and the complexes [{(Me3Si)2HCPC(R1,R2)–C(R3,R4}W(CO)5] ( 4 , 7 a , b , 9 a , b , 11 a , b ) ( 4 (trans): R1,R3 = Ph, R2,R4 = H, 7 a , b (cis, meso and rac): R1,R3 = Ph, R2,R4 = H, 9 a , b (RR und SS): R1 = Ph, R2,R3,R4 = H, 11 a , b : R1=R3 = (CH2)4, R2,R4 = H). Spectroscopic and mass spectrometric data are discussed. The structure of the complex 9 a was determined by X‐ray single crystal structure analysis showing characteristic data for the phosphirane ring such as a narrow angle at phosphorus (49,2(2)°), different P–C distances (P–C(6) 182,1(5) and P–C(7) 185,2(4) pm) and 152,9(6) pm for the basal C–C bond. 相似文献
A wide variety of planar chiral cyclopalladated compounds of general formulae [Pd{[(η5-C5H3)–CHN–CH(Me)–C10H7]Fe(η5-C5H5)}Cl(L)] (with L=py-d5 or PPh3), [Pd{[(η5-C5H3)–CHN–CH(Me)–C10H7]Fe(η5-C5H5)}(acac)] or [Pd{[(R1–CC–R2)2(η5-C5H3)–CHN–CH(Me)–C10H7]Fe(η5-C5H5)}Cl] (with R1=R2=Et; R1=Me, R2=Ph; R1=H, R2=Ph; R1=R2=Ph; R1=R2=CO2Me or R1=CO2Et, R2=Ph) are reported. The diastereomers {(Rp,R) and (Sp,R)} of these compounds have been isolated by either column chromatography or fractional crystallization. The free ligand (R)-(+)-[{(η5-C5H4)–CHN–CH(Me)–C10H7}Fe(η5–C5H5)] (1) and compound (+)-(Rp,R)-[Pd{[(Et–CC–Et)2(η5-C5H3)–CHN–CH(Me)–C10H7]Fe(η5-C5H5)}Cl] (7a) have also been characterized by X-ray diffraction. Electrochemical studies based on cyclic voltammetries of all the compounds are also reported. 相似文献
Abstract Compounds of the following structure (R1O)2(X)P[sbnd]Y–P(X)(OR2)2 (X = O, Y = Sn (n = 1–4), R1 = R2 = Me, iPr; X = S, Y = Sn (n = 1–4), R1, R2 = Me, Et, iPr, iBu; X = S, Y = S-Se-S, S-Te-S, R1 = R2 = Me were prepared and their NMR spectra were analysed. Depending on the number of sulfur atoms, bonded between the phosphorus atoms, typical ranges of the P-P coupling constants were found for the different sulfanes investigated: 2JPP from-10 to-20 Hz, 3JPP less than 3 Hz, 4JPP from +10 to +13 Hz and 5JPP less than 1 Hz. For the small vicinal coupling constants and the relatively large values of 4JPP different possibilities of their interpretation are given. 相似文献
N–O Bond Cleavage in O-silylated Oximes by Reaction with a Titanocene-Alkyne Complex Cp2Ti(Me3SiC2SiMe3) 1 reacts with alicyclic and aliphatic O-silylated ketoximes of type R1R2C=NOSiMe3 ( 2 : R1R2 = (CH2)5; 3 : R1 = R2 = Me) under N–O bond breaking to the titanocene complexes Cp2Ti(OSiMe3)(N=CR1R2) 6 (R1R2 = (CH2)5) and 7 (R1 = R2 = Me). The structure of 6 was obtained by X-ray crystal structure analysis ( 6 : triclinic, space group P1, Z = 2, a = 9.486(1), b = 9.865(1), c = 12.305(2) Å, α = 107.19(1), β = 96.08(1), γ = 111.08(1)°). 相似文献
Treatment of methylene dioximes (I) with palladium(II) chloride gives [(R1R2C=NO)2CH2]PdCl2 (II), their 1H NMR spectra exhibit resonances due to one of the methylene protons in remarkably lower fields (σ 8.99—8.28 ppm). X-ray analysis of IIb (R1 = R2 = n-Pr) shows that the ligand has boat-like conformation in which the distance between the Pd and the H atom of the OCH2O-group is 2.46 Å, being much less than expected for the sum of the Van der Waals radii. 相似文献
Nucleophilic substitution reactions of various acetylides on substituted tricarbonyl(η6-fluoroarene)chromiums were pursued. The reaction presumably underwent a more complicated mechanism rather than the direct substitution on the fluorine-bearing carbon. The organometallic compounds (η6-C6H3R1R2R3)Cr(CO)3 (R1: CC–C6H4CH3, R2: o-Me, R3: H (5a), R1: CC–C6H4CH3, R2: o-OMe, R3: H (6a), R1: CC–C6H4CH3, R2: m-OMe, R3: H (6b), R1: CCPh, R2: o-Me, R3: o-OMe (8b), R1: CCPh, R2: m-Me, R3: m-OMe (8c), R1: CCSiMe3, R2: o-Me, R3: H (9a), R1: CC–C6H4CCH, R2: H, R3: H (12), R1: CC–C6H4CCH, R2: o-Me, R3: H (13)) as well as the organometallic dimmer [{(η6-o-Me-C6H4)Cr(CO)3(di-ethynyl)] (di-ethynyl: CC–C6H4CC (14)) have been synthesized from nucleophilic substitution reactions of tricarbonyl(η6-fluoroarene)(chromium) compounds with suitable acetylides. The products have been characterized by spectroscopic means. In addition, (8b) and (8c) were characterized by X-ray diffraction studies. Further reactions of (9a) and (12) with appropriate amount of Co2(CO)8 yielded μ-alkyne bridged bimetallic complexes, Co2(CO)6{μ-Me3SiCC–(o-tolueneCr(CO)3} (10) and (Co2(CO)6)2{μ-HCC–C6H4–CC–(benzene)Cr(CO)3)}(15), respectively. Both (10) and (15) were characterized by spectroscopic means as well as single crystal X-ray crystallography. The core of these molecules is quasi-tetrahedron containing a Co2C2 unit. A two-dicobalt-fragments coordinated di-enyls complex, (Co2(CO)6)2{μ-HCC–C6H4–CC–H} (17), was synthesized from the reaction of 1,3-diethynylbenzene with Co2(CO)8. Crystallographic studies of (17) also show that it exhibits a distorted Co2C2 quasi-tetrahedral geometry. 相似文献
Nine new organoammonium violurates [R1R2R3NH][C4H2N3O4] [R1 = R2 = H, R3 = c‐C3H5 ( 2 ), R3 = tBu ( 3 ), R3 = adamantyl ( 4 ), R3 = C6H2Me2‐4,5‐NH2‐2 ( 5 ); R1 = H, R2 = R3 = Et ( 6 ), iPr ( 7 ); R1 = H, R2/R3 = (–CH2–)4 ( 8 ); R1 = R2 = R3 = Et ( 9 ); R1 = R2 = Me, R3 = (CH2)2NMe2 ( 10 )] were prepared by treatment of violuric acid ( 1 ) with a variety of primary, secondary, and tertiary amines. With the exception of orange 5 , all these violurate salts form bright blue or blue‐purple crystalline solids. The acidic triethylammonium violurate [NHEt3]H[C4H2N3O4]2 · H2O ( 9a ) was isolated in the form of red‐violet, plate‐like crystals by the reaction of violuric acid hydrate with triethylamine in a molar ratio of 2:1 in ethanol. All compounds were fully characterized by their IR and NMR (1H, 13C) data as well as elemental analyses. X‐ray crystal structures determinations of 2 , 7 , and 9a revealed supramolecular self‐assembly through networks of N–H ··· N and N–H ··· O hydrogen bonds in the crystalline state. 相似文献
Element-Organic Amine/Imine Compounds, XXXI. - Cyclometallation with N-tert-Butyl-Phosphorus-Nitrogen Iridium Complexes The interaction of R1R2N–PNR3 ( 1 ) (R1 SiMe3, tBu, iC3H7; R2 R3 SiMe3, tBu) with [M(COD)(μ-Cl)]2 ( 2 ), M Rh, Ir, affords the amino(imino)phosphane complexes 3 , whose PN bond adds methanol with formation of the diamidophosphite complexes 4 . Already below 0°C the iridium compounds of 4 undergo cyclometallation of a tBu methyl group (R2) with formation of the hydrido-iridium metallaheterocycles 5 . The structures of 4b and 5a are elucidated by X-ray analyses. 相似文献
Phosphinoalkylchlorostannanes of the type Me2Sn(Cl)(CH2)nPR1R2 (n = 2,3) (I–VIII) are synthesized by a redistribution reaction of the tetraorganostannanes Me3Sn(CH2)nPR1R2 (n = 2,3) with trimethyltin chloride. In non-coordinating solvents the tin atom in I–IV is tetracoordinated, whereas NMR data indicate an intramolecular SnP interaction for V–VIII. In the solid state compound III exists as an 1:1 adduct with trimethyltin chloride. With methyl iodide compounds I–VIII form the phosphonium stannates Me2SnCl) (I) (CH2)nP+R1R2Me (XI–XIII). Compounds I–VIII are suitable starting materials for the synthesis of the tin hydrides Me2Sn(H)(CH2)nPR1R2 (XIV–XVI) and the distannanes [Me2Sn(CH2)nPR1R2]2 (XVII–XIX). The reaction of I–VIII with sodium in liquid ammonia or with lithium in THF, respectively, yields solutions of the corresponding alkali stannides Me2Sn(M)(CH2)nPR1R2 (M = Li, Na). 相似文献
The first step in the reaction of trimethylsilylmethylene-dimethylsulfurane 1 (prepared from (CH3)3SiCH2S?(CH3)2ī with 1 equivalent (CH3)3COK) with carbonyl compounds (R1)(R2)CHCOCH2R32 leads Peterson-like way to the non-isolable vinylsulfoniumdimethylsilanolate-intermediate B or its recombined product A. Depending on the reaction conditions and the nature of the substituents R1, R2 and R3 there exist five different pathways to the end products 3–7. Frequently one can find an elimination of trimethylsilanole followed by a 2,3-sigmatropic rearrangement of an allyl-substituted methylene - sulfurane - intermediate to the 2,3,3 - trialkyl - 5 -thiahex -1 - enes 3 [CH3SCH2C(R1)(R2)C(CH2R3)=CH2]. Sometimes this formation of 3 is suppressed by means of two equivalents of (CH3)3COK. In this case demethylation of the assumed precursor B arises yielding the E,Z-vinylsulfides 4 [CH3SCH=C(CH2R3)(CHR1R2)], whereas the formation of the methylthiomethyl-dialkylcar-binoles 5 [CH3SCH2C(OH)(CH2R3)(CHR1R2)] can be explained by the demethylation of the precursor A. Treatment with five equivalents of (CH3)3COK yields in one case the 2,2,5,7 - tetramethyl - 5 - hydroxy - 3 - oxaoctane (7a) as a consequence of a extrusion of dimethylsulfide. Frequently also epoxides of type 6 [CH2-C(CH2R3)(CHR1R2)] can be isolated. Their formation is compared with the well-known preparation of epoxides by the dimethylsulfonium-methylide on the one and dimethylsulfoxoniummethylide on the other side. 相似文献
Carbon-13 chemical shifts and J(PC) coupling constants of 29 vinyl phosphate derivatives are presented. In the series of compounds (R1O)2P(O)OC1(R)?C2X2 (where 3 in R indicates the first carbon of the R2 substituent) large differences were found between the 3J(P, O, C-1, C-3) and 3J(P, O, C-1, C-2) coupling constants of the chlorinated (X?CI) and the unsubstituted (X?H) derivatives. A possible explanation of this phenomenon is given on the basis of Jameson's s bond character theory. Strong stereospecificity of 3J(P, O, C-1, C-3) coupling constants was observed in the series of compounds (R1O)2 P(O)OC1(R)?C2HR3. Coupling constants varied between 3.2–4.9 Hz in the E isomers, while peaks could not be resolved in the Z isomers. The 3J(P, O, C-1, C-2) coupling constants were regularly 20–30% greater in the Z than in the E isomers. 相似文献
This work highlights the role of synthetic carrier (ionophore) in the separation of heavy metal ions. A new series of ionophores; 4,4′-nitrophenyl-azo-O,O′-phenyl-3,6,9-trioxaundecane-1,10-dioate (R1), bis[4,4′nitro-phenylazo-naphthyl-(2,2-dioxydiethylether)] (R2) 1,8-bis-(2-naphthyloxy)-3,6-dioxaoctane (R3), 1,11-bis-(2-naphthyloxy)-3,6,9-trioxaunde-cane (R4), 1,5-bis-(2-naphthyloxy)-3-oxa-pentane (R5) have been synthesized and used as extractant as well as carrier for the transport of various metal ions (Na+, K+, Mg2+, Ni2+, Cu2+ and Zn2+) through liquid membranes. Effect of various parameters such as metal ion concentration, ionophore concentration, liquid–liquid extraction, back extraction, comparison of transport efficiency of BLM and SLM and different membrane support (hen’s egg shell and PTFE) have been studied. In BLM ionophores (R2–R5) transport Zn+ at greater extent and the observed trend for the transport of Zn2+ is R2?>?R4?>?R3?>?R5 respectively. Further transport efficiency is increased in SLM. In egg shell membrane ionophores (R2–R5) transport Zn+ due to their non-cyclic structure and pseudo cavity formation while ionophore R1 transports Cu2+ ions at greater extent due to its cyclic structure and cavity size. Among the membrane support used egg shell membrane is found best for the transport of zinc ions because of its hydrophobic nature and exhibits electrostatic interactions between positively charged zinc ions and –COOH group of egg shell membrane. Thus structure of ionophores, hydrophobicity and porosity of the membrane support plays important role in separation of metal ions. 相似文献
In this work, we describe the syntheses, characterization, and antifungal activity of [In{S2CNR(R1)}3] (1), [Ga{S2CNR(R1)}3] (2), [Bi{S2CNR(R1)}3] (3), [In{S2CNR(R2)}3] (4), [Ga{S2CNR(R2)}3] (5), and [Bi{S2CNR(R2)}3] (6) {R?=?Me; R1?=?CH2CH(OMe)2; and R2?=?2-methyl-1,3-dioxolane}. All complexes have been characterized using infrared and 1H and 13C spectroscopy, and the structures of 1, 3, 4, and 6 have been authenticated by X-ray diffraction. The In(III)–dithiocarbamate bonding scheme depicts a distorted octahedral with asymmetric In(III)–S bonds and S–In–S angles. A pentagonal bipyramid is observed for the corresponding Bi(III) complexes with intermolecular Bi–S associations through the lone pair of electrons. The antifungal activities of 1–6 have been screened against Aspergillus niger, Aspergillus parasiticus, and Penicillium citrinum, and the results have been compared with those of nystatin and miconazole nitrate, as control drugs. 相似文献
Monomeric bis(isopropoxy) titanium complexes LTi(Oi Pr)2 (L = ─ OC6H2–4‐R1–6‐R2–2‐CH2N[(CH2)2N(R3)2]CH2–4‐R4–6‐R5‐C6H2O ─ , R1 = R2 = t Bu, R3 = Et, R4 = R5 = Cl, (L1)Ti(Oi Pr)2; R1 = R2 = Me, R3 = Et, R4 = R5 = Me, (L2)Ti(Oi Pr)2; R1 = R2 = t Bu, R3 = Et, R4 = OMe, R5 = t Bu, (L3)Ti(Oi Pr)2; R1 = R4 = OMe, R3 = Et, R2 = R5 = t Bu, (L4)Ti(Oi Pr)2; R1 = R2 = t Bu, R3 = Me, R4 = OMe, R5 = t Bu, (L5)Ti(Oi Pr)2) supported by amine bis(phenolate) ligands were synthesized and characterized using NMR spectroscopy and elemental analysis. The solid‐state structure of (L3)Ti(Oi Pr)2 was determined using single‐crystal X‐ray diffraction. (L1–5)Ti(Oi Pr)2 were all found to initiate the ring‐opening polymerization of l ‐lactide and rac ‐lactide in a controlled manner at 110–160°C. As shown by kinetic studies, (L1)Ti(Oi Pr)2 polymerized l ‐lactide faster than did (L2–5)Ti(Oi Pr)2. In addition, good number‐average molecular weight and narrow polydispersity index (1.00–1.71) of polymers were also obtained. The microstructure of the polymers and a possible mechanism of coordination–insertion of polymerization were evidenced by MALDI‐TOF and 1H NMR spectra of the polylactides. 相似文献
Polysulfonyl Amines. VII. Aliphatic Trisulfonyl Amines The compounds N(SO2R1)2(SO2R2) with R1 = R2 = CH3 ( 2a ), R1 = R2 = C2H5 ( 2b ) and R1 = CH3, R2 = C2H5 ( 2c ) are prepared by cleavage of aminostannanes (CH3)3SnN(SO2R1)2 with sulfonyl chlorides R2SO2Cl. A simple synthesis of 2a from AgN(SO2CH3)2 and CH3SO2Cl is described. From the vibrational spectra of 2a , evidence is obtained for a planar NS3 group in this compound. X-ray structure determinations of 2b and HN(SO2C2H5)2 ( 3 ) are reported. In 2b , the NS3 group is approximately planar (S? N? S bond angles 119.0 ± 0.6°, sum of bond angles at N 356.9°); the S? N bond lengths of ca. 173 pm indicate a bond order of 1. In compound 3 , the nitrogen atom has a planar coordination (S? N? S angle 125.3°, sum of bond angles at N 359.3°), the S? N bond lengths of ca. 165 pm correlate with a bond order of 1.3? 1.4. 相似文献
Five bis(quinolylmethyl)‐(1H ‐indolylmethyl)amine (BQIA) compounds, that is, {(quinol‐8‐yl‐CH2)2NCH2(3‐Br‐1H ‐indol‐2‐yl)} ( L1H ) and {[(8‐R3‐quinol‐2‐yl)CH2]2NCH(R2)[3‐R1‐1H ‐indol‐2‐yl]} ( L2–5H ) ( L2H : R1=Br, R2=H, R3=H; L3H : R1=Br, R2=H, R3=i Pr; L4H : R1=H, R2=CH3, R3=i Pr; L5H : R1=H, R2=n Bu, R3=i Pr) were synthesized and used to prepare calcium complexes. The reactions of L1–5H with silylamido calcium precursors (Ca[N(SiMe2R)2]2(THF)2, R=Me or H) at room temperature gave heteroleptic products ( L1, 2 )CaN(SiMe3)2 ( 1 , 2 ), ( L3, 4 )CaN(SiHMe2)2 ( 3 a , 4 a ) and homoleptic complexes ( L3, 5 )2Ca ( D3 , D5 ). NMR and X‐ray analyses proved that these calcium complexes were stabilized through Ca⋅⋅⋅C−Si, Ca⋅⋅⋅H−Si or Ca⋅⋅⋅H−C agostic interactions. Unexpectedly, calcium complexes (( L3–5 )CaN(SiMe3)2) bearing more sterically encumbered ligands of the same type were extremely unstable and underwent C−N bond cleavage processes as a consequence of intramolecular C−H bond activation, leading to the exclusive formation of (E )‐1,2‐bis(8‐isopropylquinol‐2‐yl)ethane. 相似文献
Phosphino derivatives of serine R2P–CH2–CH(NHBOC)(COOMe) ( 2 a – 2 d ) have been obtained in high yield by nucleophilic phosphination of N‐(tert.butoxycarbonyl)‐3‐iodo‐L‐alanine methylester with secondary phosphines R2PH (R = Ph, 2‐tolyl, 3,5‐xylyl, cyclohexyl) in DMF using potassium carbonate as the base. Deprotection of 2 b with HCl affords the amino acid ester hydrochloride [2‐Tol2P–CH2–CH(NH3)(COOMe)]+Cl– ( 3 a ). The X‐ray structures of 2 a (space group P21/n) and 2 c (space group P 1) have been determined. The two enantiomers of 2 a or 2 c are interconnected by N–H…O hydrogen bridges forming dimers in the solid state. 相似文献
Binuclear Nickel(II) Complexes with Oxalamidinates as Bridging Ligands: Synthesis and Struktures of Compounds with Planar, Tetrahedral, Tetragonal‐pyramidal, and Octahedral Coordination Oxalamidines R1–NH–C(=NR2–C(=NR2)–NH–R1 react selectively with Ni(acac)2 under formation of the planar complexes [(acac)Ni(oxalamidinate)Ni(acac)]. Two crystal structures of the binuclear complexes with R = R′ = Ph ( 1 ) or p‐tolyl ( 2 ) show that the bridging oxalamidinates bind as bidendate ligands at each Nickel(II) atom. In contrast, the more sterically demanding fragment (Ph3P)NiBr can only coordinate at sterically less demanding oxalamidinates to form complexes of the type [(Ph3P)NiBr]2(oxalamidinate) with tetrahedral coordination of NiII found by X‐ray analyses. Oxalamidines containing additional donor atoms in the side arms react very different, but in each case under formation of binuclear complexes, such as [(acac)2Ni]2( H2E ) ( 8 ) (with R1: –(CH2)3PPh2, R2: p‐tolyl) in which the oxalamidine acts as bidentate neutral P,N‐ligand and the NiII atom has an octahedral environment. H2F (with R1: –(CH2)3PPh2, R2: Mesityl), however, yields the planar complex [(acac)Ni]2( F ) ( 9 ) with dianionic oxalamidinate under elimination of acetylacetone. There is no coordination of the donor groups of the side arms in the solid state of complex 9 , in contrast to the analogous binuclear complex [(acac)Ni]2( H ) 10 (R1: –CH2–CH2‐2‐pyridyl, R2: Mesityl). In this complex a distorted tetragonal‐pyramidal coordination of NiII is achieved. 2 reacts with an excess of LiCH3 under elimination of the oxalamidinate to form the cluster compound Li4(THF)4Ni2Me8 in very good yields, while 9 yields the THF poorer cluster Li2(THF)2Li2Ni2Me8 under similar conditions. 相似文献