共查询到20条相似文献,搜索用时 31 毫秒
1.
《Journal of organometallic chemistry》2010,695(24):2651-2657
Aminotin(II and IV) compounds {[(2,6-i-Pr-C6H3)(H)N]-μ-(Sn)-Cl}2, {2-[(CH3)2NCH2]C6H4}2Sn[N(H)(2,6-i-Pr-C6H3)]2 and {2-[(CH3)2NCH2]C6H4}Sn[N(2,6-i-Pr-C6H3)(SiMe3)] were prepared by lithium halide elimination from tin halides and corresponding lithium complexes. [(2,6-i-Pr-C6H3)(H)N]Li (1) reacts with one half of molar equivalent of SnCl2 to give {[(2,6-i-Pr-C6H3)(H)N]-μ-(Sn)-Cl}2. The same lithium amide (1) gave with R3SnCl corresponding aminostannanes. Further reactions of these compounds with n-butyllithium gave the starting 1 and tetraorganostannanes. {2-[(CH3)2NCH2]C6H4}2SnBr2 reacts with two equivalents of 1 to {2-[(CH3)2NCH2]C6H4}2Sn[N(H)(2,6-i-Pr-C6H3)]2. The dimeric heteroleptic stannylene {[(2,6-i-Pr-C6H3)(SiMe3)N](μ2-Cl)Sn}2 reacts with 2-[(CH3)2NCH2]C6H4Li to the monomeric {2-[(CH3)2NCH2]C6H4}Sn[N(2,6-i-Pr-C6H3)(SiMe3)]. The structure in the solid state and in solution and reactivity of products is also discussed. The unique decatin cluster has been isolated by hydrolysis of {[(2,6-i-Pr-C6H3)(H)N]-μ-(Sn)-Cl}2. The structure of some compounds was also evaluated by theoretical DFT methods. 相似文献
2.
Jan Chalupa Karel Handlíř Zdeňka Padělková Marcela Vejsová Vladimír Buchta Robert Jirásko Aleš Rûžička 《应用有机金属化学》2008,22(6):308-313
The set of four triorganotin(IV) diesters of 4‐ketopimelic acid containing {2‐[(CH3)2NCH2]C6H4}‐ as a C,N‐chelating ligand was prepared. Their structures were studied by the help of IR, NMR and X‐ray crystallographic techniques in the case of {{2‐[(CH3)2NCH2]C6H4}SnPh2}2[(OOCCH2CH2)2C?]. All these compounds are monomeric both in solid state and solution with five‐coordinated tin atoms and medium strong intramolecular Sn? N connection. The antimycotical activity of these compound was studied and compared with the triorganotin(IV) derivatives of 4‐ketopimelic acid and antimycotical drugs in clinical use. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
3.
Antonius F.M.J. Van Der Ploeg Gerard Van Koten Kees Vrieze 《Journal of organometallic chemistry》1981,222(1):155-174
A study has been made of reactions involving organometallic compounds containing ortho-Me2NCH2 substituted aryl ligands. The single step syntheses of the new compounds [(2-Me2NCH2C6H4)2TlCl], [ [{(S)-2-Me2NCH(Me)C6H4}2TlCl], [{(S)-2-Me2NCH(Me)C6H4}TlCl2], [{2,6-(Me2NCH2)2C6H3}TlClBr] and [{2,6-(Me2NCH2)2C6H3}HgCl] are described. Stable internal NTl coordination at low temperatures has been established for the C-chiral thallium compounds. Reactions of the other Tl and Hg compounds and of [(2-Me2NCH2C6H4)2Hg] with Pd(O2CMe)2, and also of the reverse reaction of cis-[(2-Me2NCH2C6H4)2Pd] with Hg(O2CR)2 or Tl(O2CR)3, gave transmetallation of one organo ligand and led to a single mono-organopalladium compound and corresponding by-products. Reaction of cis-[(2-Me2NCH2C6H4)2Pd] with Pd(O2CR)2 gave the dimeric compound [{(2-Me2NCH2C6H4)Pd(O2CR)}2]. cis-[(2-Me2NCH2C6H4)2Pt] did not react with Pd(O2CMe)2, while reaction of trans-[(2-Me2NCH2C6H4)2Pt] or cis-[(2-Me2NC6H4CH2)2Pt] with Pd(O2CMe)2 resulted in decomposition. Upon heating, trans-[(2-Me2NCH2C6H4)2Pt] was isomerized to cis-isomer. A redox reaction between [(2-Me2NCH2C6H4)2Hg] and [Pt(COD)2] (COD 1,5-cyclo-octadiene) and [Pd2(DBA)3] (DBA dibenzylideneacetone) gave the cis-isomers of [(2-Me2NCH2C6H4)2M] (M Pd, Pt).The results are discussed in terms of influence of internal coordination of the CH2NMe2 group. It is concluded that although internal coordination of the CH2NMe2 ligand can stabilize metal—carbon bonds it cannot prevent cleavage of such bonds by electrophiles. In this respect, there is no difference in the behaviour of Hg(O2CR)2 and Tl(O2CR)3. The reactions are influenced by the metal—nitrogen bond strength, which follows the order PtN > PdN > HgN, TlN. The reactivity of Pt compounds is greatly influenced by their structure and type of ligand. It is proposed that cleavege of PdC bonds occurs mainly by a mechanism involving direct electrophilic attack at the carbon centre. 相似文献
4.
{2‐(N,N‐Dimethylaminomethyl)phenyl}(di‐t‐butyl)tin(IV)chloride, {2‐[(CH3)2NCH2]C6H4}Sn(t‐Bu)2 Cl, has been prepared and characterized using NMR and crystallography. This is the first example of a triorganotin(IV) halide containing the 2‐[(CH3)2NCH2]C6H4—group as a C,N‐chelating ligand with a weak intramolecular Sn—N interaction because of the steric hindrance of t‐butyl groups. The interatomic Sn—N distance is elongated to 2.904(14) Å and the central tin atom is distorted trigonal bipyramidal. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
5.
Nandu Bala Sharma Jayshree Shahani Renu Aggrawal Anirudh Singh 《Transition Metal Chemistry》2006,31(7):882-888
Interesting varieties of heterobimetallic mixed-ligand complexes [Zr{M(OPri)
n
}2 (L)] (where M = Al, n = 4, L = OC6H4CH = NCH2CH2O (1); M = Nb, n = 6, L = OC6H4CH = NCH2CH2O (2); M = Al, n = 4, L = OC10H6CH = NCH2CH2O (3); M = Nb, n = 6, L = OC10H6CH = NCH2CH2O (4)), [Zr{Al(OPri)4}2Cl(OAr)] (where Ar = C6H3Me2-2,5 (5); Ar = C6H2Me-4-Bu2-2,6 (6), [Zr{Al(OPri)4}2(OAr)2] (where Ar = C6H3Me2-2,5 (7); Ar = C6H2Me-4-Bu2-2,6 (8), [Zr{Al(OPri)4}3(OAr)] (where Ar = C6H3Me2-2,5 (9); Ar = C6H3Me2-2,6 (10), [ZrAl(OPri)7-n
(ON=CMe2)
n
] (where n = 4 (11); n = 7 (12), [ZrAl2(OPri)10-n
(ON=CMe2)
n
] (where n = 4 (13); n = 6 (14); n = 10 (15) and [Zr{Al(OPri)4}2{ON=CMe(R)}
n
Cl2–n] [where n = 1, R = Me (16); n = 2, R = Me (17); n = 1, R = Et (18); n = 2, R = Et (19)] have been prepared either by the salt elimination method or by alkoxide-ligand exchange. All of these heterobimetallic complexes
have been characterized by elemental analyses, molecular weight measurements, and spectroscopic (I.r., 1H-, and 27Al- n.m.r.) studies. 相似文献
6.
{2-[(CH3)2NCH2]C6H4}(n-Bu)2SnF (1) reacts with various chloroformates, acyl chlorides, methanesulfonyl chloride, 4,4′-dimethoxytrityl chloride and phosgene precursors or derivatives to form fluorinated analogues. All reactions proceed rapidly and under mild conditions. The use of a catalytic amount of 1 and KF in toluene led to a relatively high yield of a selected fluoroformate. 相似文献
7.
Maura Pellei Simone Alidori Giancarlo Gioia Lobbia Gaia Emanuela Gioia Lobbia 《Journal of organometallic chemistry》2008,693(6):996-1004
The new sodium bis(1-methyl-1H-imidazol-2-ylthio)acetate, Na[(S-tim)2CHCO2], has been prepared in ethanol solution using 2-mercapto-1-methylimidazole, dibromoacetic acid and NaOH. New di- and tri-organotin(IV) derivatives have been synthesized from reaction between SnRnCl4−n (R = Ph, Cy and nBu, n = 2-3) acceptors and Na[(S-tim)2CHCO2]. Complexes of the type {[κ1O-(S-tim)2CHCO2]SnR3} and related decarboxylated species {[κ2N,N-(S-tim)2CH2]SnR2Cl2} have been obtained and characterized by elemental analyses, FT-IR, ESIMS and multinuclear (1H, 13C and 119Sn) NMR spectral data. The adduct {κ1O-[(S-tim)2CHCO2]Sn(H2O)(C4H9)3} was characterized by single crystal X-ray studies. The dichloromethane reaction solution of {κ1O-[(S-tim)2CHCO2]Sn(C6H5)3} was re-crystallized and the decarboxylated species {[(S-tim)2CH2]SnCl(H2O)(C6H5)3} was obtained as a crystalline solid and characterized by X-ray crystallography. 相似文献
8.
Liqing Ma 《Journal of organometallic chemistry》2007,692(24):5331-5338
The reaction of 2,6-(2-{Me2NCH2}C6H4)2C6H3I (2) with Pd2(dba)3 produced the NCN diamine pincer complex [2,6-(2-Me2{NCH2}C6H4)2C6H3PdI] (3) by an oxidative addition route. The structural analysis of ligand precursor 2 revealed a syn-conformation in the solid state. Single crystal X-ray analysis of complex 3 revealed a conventional square planar geometry about the palladium center and a global C2 symmetric structure. Variable temperature and concentration NMR spectroscopic studies of complex 3 suggest an equilibrium between 3 and the dinuclear species [{2,6-(2-{Me2NCH2}C6H4)2C6H3Pd}2μ2-I]I in CDCl3 solution. An unusual carbonate complex [{2,6-(2-{Me2NCH2}C6H4)2C6H3Pd}3μ3-CO3]I3 (4) was also structurally characterized as a minor product during synthesis of 3. 相似文献
9.
Organoselenium compounds containing pyrazole or phenylthiazole groups: Synthesis,structure, tin(IV) complexes and antiproliferative activity
下载免费PDF全文
![点击此处可从《应用有机金属化学》网站下载免费的PDF全文](/ch/ext_images/free.gif)
The diorganodiselenides (pzCH2CH2)2Se2 ( 1 ) and (PhtzCH2)2Se2 ( 2 ) were prepared by reacting Na2Se2 with 1‐(2‐bromoethyl)‐1H‐pyrazole and 4‐(chloromethyl)‐2‐phenylthiazole, respectively, while the reactions between 1‐(2‐bromoethyl)‐1H‐pyrazole or 4‐(chloromethyl)‐2‐phenylthiazole and the lithium organoselenolates [2‐(Et2NCH2)C6H4]SeLi and [2‐{O(CH2CH2)2NCH2}C6H4]SeLi in a 1:1 molar ratio resulted in the heteroleptic diorganoselenium(II) compounds [2‐(Et2NCH2)C6H4](R)Se (R = pzCH2CH2 ( 3 ) or PhtzCH2 ( 5 )) and [2‐{O(CH2CH2)2NCH2}C6H4](R)Se (R = pzCH2CH2 ( 4 ) or PhtzCH2 ( 6 )). The diorganotin(IV) bis(organoselenolato) derivatives of type R2Sn(SeCH2CH2pz)2 (R = 2‐(Me2NCH2)C6H4 ( 7 ) or Me ( 8 )) were obtained by reacting (pzCH2CH2)SeNa with the appropriate diorganotin(IV)dichloride in a 2:1 molar ratio. All compounds were investigated using NMR spectroscopy (1H, 13C, 77Se, 119Sn as appropriate) and ESI+ mass spectrometry. The molecular structures of 2 and 6 were determined using single‐crystal X‐ray diffraction. The formation of a 10–Se–3 hypercoordinated species was evidenced for 6 in the solid state, as a consequence of the C,N coordination behaviour of the 2‐{O(CH2CH2)2NCH2}C6H4 group. Compounds 1 , 7 and 8 were investigated for their antiproliferative activity towards the mouse colon carcinoma C26 cell line with the preliminary results showing a better activity than 5‐fluorouracil. 相似文献
10.
The stannylene {2-[(CH3)2NCH2]C6H4}2Sn (1) was reacted with oxygen, sulfur, selenium, tellurium, and carbon disulfide. The reactions with heavier chalcogens led to the rapid formation of 1:1 dinuclear adducts which were characterized by elemental analysis, ESI-MS measurements, 1H NMR spectroscopy, and structurally characterized by X-ray diffraction (in the case of reaction products with S8 (3) and Te (5)). The reaction of 1 with carbon disulfide and elemental sulfur yields the remarkable compound {{2-[(CH3)2NCH2]2C6H4}Sn}2(μ2-S2CCS2) (3a). The stability and reactivity of compounds 1-5 were rationalized at DFT/TZ2P level. 相似文献
11.
采用密度泛函理论(DFT)研究了螺桨烷型分子BX[(CH2)n]3和BX(CH2)[CH(CH2)n CH](X=N,P;n=1-6)的结构、稳定性、化学键和电子光谱性质.计算结果表明这些分子都是稳定的.BX[(CH2)n]3(X=N,P;n=1-6)的最高占据分子轨道(HOMO)和最低空分子轨道(LUMO)之间的能隙均大于5.20 eV,其中BN[CH2]3和BP[CH2]3的能隙超过7.0 eV,与C5H6的能隙(7.27 eV)很接近,BX(CH2)[CH(CH2)n CH](X=N,P;n=1-6)的能隙在6.80 eV左右.所研究分子能量的二阶差分表明BN[(CH2)3]3、BP[(CH2)4]3及BX(CH2)[CH(CH2)2CH](X=N,P)是最稳定的.BX[(CH2)n]3的Wiberg键级表明除了BN[(CH2)n]3(n=2和6)中不存在B―N键,其它化合物中B和N均形成了化学键,BP[(CH2)n]3中除了BP[(CH2)2]3不存在B―P键,其它的均存在.电子密度的拓扑分析表明N―B键属于离子键,而P―B键具有共价键特征.BX[(CH2)n]3(X=N,P)的第一垂直激发能分别在191.1-284.8 nm和191.8-270.1 nm之间,BX(CH2)[CH(CH2)n CH](X=N,P)的第一垂直激发能分别在190.5-199.7 nm和209.0-221.3 nm之间. 相似文献
12.
Alpar Pöllnitz Vito Lippolis Massimiliano Arca Anca Silvestru 《Journal of organometallic chemistry》2011,696(15-16):2837-2844
Cleavage of the Se–Se bond in [2-(Et2NCH2)C6H4]2Se2 (1) with SO2Cl2 (1:1 molar ratio) yielded the organoselenium(II) chloride [2-(Et2NCH2)C6H4]SeCl (2). Treatment of 2 with excess of KX yielded the organoselenium(II) halides [2-(Et2NCH2)C6H4]SeX [X = Br (3), I (4)]. The new compounds 2–4 were characterized by solution NMR spectroscopy (1H, 13C, 77Se, 2D experiments). The solid-state molecular structures of 2, 2·HCl and 3 were established by single crystal X-ray diffraction. Distorted T-shaped coordination geometries of type (C,N)SeX (X = Cl, Br) and CSeCl2 were found for the neutral halides 2 and 3, and the zwitterionic species [2-{Et2N+(H)CH2}C6H4]SeCl2 ̄ (2·HCl), respectively. DFT calculations were performed on 2–4 and the related tellurium compounds [2-(Et2NCH2)C6H4]TeX [X = Cl (5), Br (6) and I (7)] in order to elucidate the bond nature and FT-Raman features of this class of organochalcogen(II) derivatives. 相似文献
13.
Christina Dietz Jana Martincová Bernard Mahieu Roman Jambor Sonja Herres‐Pawlis Klaus Jurkschat 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(21):6695-6708
The syntheses of the transition metal complexes cis‐[(4‐tBu‐2,6‐{P(O)(OiPr)2}2C6H2SnCl)2MX2] ( 1 , M=Pd, X=Cl; 2 , M=Pd, X=Br; 3 , M=Pd, X=I; 4 , M=Pt, X=Cl), cis‐[{2,6‐(Me2NCH2)2C6H3SnCl}2MX2] ( 5 , M=Pd, X=I; 6 , M=Pt, X=Cl), trans‐[{2,6‐(Me2NCH2)2C6H3SnI}2PtI2] ( 7 ) and trans‐[(4‐tBu‐2,6‐{P(O)(OiPr)2}2 C6H2SnCl)PdI2]2 ( 8 ) are reported. Also reported is the serendipitous formation of the unprecedented complexes trans‐[(4‐tBu‐2,6‐{P(O)(OiPr)2}2C6H2SnCl)2 Pt(SnCl3)2] ( 10 ) and [(4‐tBu‐2,6‐{P(O) (OiPr)2}2C6H2SnCl)3Pt(SnCl3)2] ( 11 ). The compounds were characterised by elemental analyses, 1H, 13C, 31P, 119Sn and 195Pt NMR spectroscopy, single‐crystal X‐ray diffraction analysis, UV/Vis spectroscopy and, in the cases of compounds 1 , 3 and 4 , also by Mössbauer spectroscopy. All the compounds show the tin atoms in a distorted trigonal‐bipyramidal environment. The Mössbauer spectra suggest the tin atoms to be present in the oxidation state III. The kinetic lability of the complexes was studied by redistribution reactions between compounds 1 and 3 as well as between 1 and cis‐[{2,6‐(Me2NCH2)2C6H3SnCl}2PdCl2]. DFT calculations provided insights into both the bonding situation of the compounds and the energy difference between the cis and trans isomers. The latter is influenced by the donor strength of the pincer‐type ligands. 相似文献
14.
Phosphonic acids [(HO)2P(O)C2H4CnF2n+1] (n = 4, 6) and [(HO)2P(O)C6H4-4-CnF2n+1] (n = 0, 1, 6) have been prepared in good yields. Deprotonation and reaction with cis-[PtCl2(PPh3)2] affords fluorinated platinum complexes which have been characterised by elemental analysis, mass spectrometry, IR and NMR spectroscopies. The structures of [Pt{O2P(O)C6H4-4-F}(PPh3)2], [Pt{O2P(O)C6H4-4-CF3}(PPh3)2] and [Pt{O2P(O)C2H4C6F13}(PPh3)2] have been determined by single crystal X-ray diffraction. 相似文献
15.
The reactions of substituted N-sulfinylanilines with the complexes {Pt[P(C6H53]2O2} and {IrClCO[P(C6H5)3]2} have been reinvestigated. The former complex yields {Pt[P(C6H5)3]2SO4} as the only isolable product in reactions with N-sulfinylaniline. In contrast to a previous report, Vaska's complex has been found not to react with C6H5NSO under anhydrous conditions. {Pt[P(C6H5)3]2-(C2H4)} reacts with N-sulfinyl compounds to give complexes of formula {Pt[P(C6H5)3]2-(RNSO)} where R = C6H5, p-O2NC6H4, p-CH3C6H4, or p-CH3C6H4SO2. {Pt[P(C6H5)3]3} reacts with C6H5NSO to give the same product obtained from reaction with the ethylene complex. Vaska's complex and its bromo analog form 1:1 adducts with p-O2NC6H4NSO. 相似文献
16.
A.F.M.J. van der Ploeg G. van Koten K. Vrieze 《Journal of organometallic chemistry》1982,226(1):93-103
Complexes [{2,6-(Me2NCH2)2C6H3} (p-tolylNYNR)PtHgBrCl] (Y CH, N; R Me, Et, i-Pr) have been prepared by the reaction of [{2,6-(Me2NCH2)2C6H3}-PtBr] with [Hg(p-tolylNYNR)Cl]. Similar complexes were obtained, although in lower yields, from exchange reactions of [{2,6-(Me2NCH2)2C6H3} (RCO2)-PtHg(O2CR)Br] with p-tolylNNN(H)-p-tolyl and p-tolylNC(H)N(H)Et.The proposed structure for these heterodinuclear compounds involves a Pt-to-Hg donor bond which is bridged by a triazenido (Y N) or a formamidino (Y CH) group, the five-membered ring thus formed acting as a stabilizing factor. The absence of a subsequent electron transfer reaction is ascribed to the constraints of the terdentate 2,6-(Me2NCH2)2C6H3 ligand, which fixes the N-donor atoms in mutual trans-positions.The use of p-tolylNYNR, where R is an alkyl group, results in the formation of two isomers of [{2,6-(Me2NCH2)2C6H3} (p-tolylNYNR)PtHgBrCl] with p-tolyl-N and alkyl-N sites bonded either to Pt or Hg. The relative abundance of these isomers varies systematically with the nature of the group R. It is suggested that the ratio is determined during the formation of the complexes and that both steric and electronic factors are important. 相似文献
17.
《Journal of organometallic chemistry》2008,693(17):2937-2941
The solid state structures of products of fluorination of LCNnBuSnCl2 (where LCN is 2-[(CH3)2NCH2]C6H4-) by different methods are reported. The reaction of 3 equiv. of [NH4]+[LCNnBuSnF3]− and Pr(OTf)3 led to dimeric arrangement [LCNnBuSnF(μ-F)2SnLCNnBuF] · 2HOTf. Two different polymorphs of polymeric [LCNnBuSnF2]n have been obtained by crystallization. Prepared compounds were studied by X-ray crystallographic methods, DSC and theoretical calculations at the B3LYP/LANL2DZ level. 相似文献
18.
Tomáš Řezníček Libor Dostál Aleš Růžička Jiří Kulhánek Filip Bureš Roman Jambor 《应用有机金属化学》2011,25(3):173-179
The phosphines L1PPh2 (1) and L2PPh2 (2) containing different Y,C,Y‐chelating ligands, L1 = 2,6‐(tBuOCH2)2C6H3? and L2 = 2,6‐(Me2NCH2)2C6H3?, were treated with PdCl2 and di‐µ‐chloro‐bis[2‐[(N,N‐dimethylamino)methyl]phenyl‐C,N]‐dipalladium(II) and yielded complexes trans‐{[2,6‐(tBuOCH2)2C6H3]PPh2}2PdCl2 (3), {[2,6‐(Me2NCH2)2C6H3]PPh2} PdCl2 (4), {[2,6‐(tBuOCH2)2C6H3]PPh2}Pd(Cl)[2‐(Me2NCH2)C6H4] (5) and {[2,6‐(Me2NCH2)2C6H3]PPh2}Pd(Cl)[2‐(Me2NCH2)C6H4] (6) as the result of different ability of starting phosphines 1 and 2 to complex PdCl2. Compounds 3–6 were characterized by 1H, 13C, 31P NMR spectroscopy and ESI‐MS. The molecular structures of 3,4 and 6 were also determined by X‐ray diffraction analysis. The catalytic activity of complexes 3–6 was evaluated in the Suzuki‐Miyaura cross‐coupling reaction. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
19.
Răzvan Şuteu Ciprian I. Raţ Cristian Silvestru Andrada Simion Natalia Candu Vasile I. Pârvulescu Anca Silvestru 《应用有机金属化学》2020,34(4):e5393
The compounds [2-(Me2NCH2)C6H4]2SbL (L = ONO2 ( 2 ), OSO2CF3 ( 3 )) and [PhCH2N(CH2C6H4)2]SbL (L = ONO2 ( 5 ), OSO2CF3 ( 6 )) were prepared by reacting [2-(Me2NCH2)C6H4]2SbCl ( 1 ) and [PhCH2N(CH2C6H4)2]SbCl ( 4 ), respectively, with the appropriate silver(I) salt in a 1:1 molar ratio. The new species 2 – 6 were structurally characterized in solution using multinuclear NMR and in the solid state using infrared spectroscopy. The solid-state structures for compounds 2 , 4 and 6, as well as for the hydrolysis ionic product [{2-(Me2N+HCH2)C6H4}{2-(Me2NCH2)C6H4}SbOH][CF3SO3]− ( 3h ) were determined using single-crystal X-ray diffraction. Medium to strong intramolecular N→ Sb interactions were observed in all these four compounds, thus resulting in hypercoordinated organoantimony(III) species 14-Sb-6 in 2 and 10-Sb-4 in the cation of 3h and in 4 and 6 . Compounds 1 – 6 and the starting amines PhCH2NMe2 and PhCH2N(CH2C6H4Br-2)2 were investigated as catalysts in the Henry (nitroaldol) addition of nitromethane to benzaldehyde. The activity of compounds 1 – 6 resulted as an effect of the cooperation of the positively charged antimony with the negatively charged nitrogen. 相似文献
20.
Anca Beleaga Monika Kulcsar Calin Deleanu Alina Nicolescu Cristian Silvestru Anca Silvestru 《Journal of organometallic chemistry》2009,694(9-10):1308-1316
Arylselenium(II) derivatives of dithiophosphorus ligands of type ArSeSP(S)R2 [Ar = Ph, R = Ph (1), OPri (2); 2-[MeN(CH2CH2)2NCH2]C6H4, R = Ph (3), OPri (4); 2-[O(CH2CH2)2NCH2]C6H4, R = OPri (6)] were prepared by redistribution reactions between Ar2Se2 and [R2P(S)S]2. The derivative [2-{O(CH2CH2)2NCH2}C6H4]SeSP(S)Ph2 (5) was obtained by the salt metathesis reaction between [2-{O(CH2CH2)2NCH2}C6H4]SeCl and NH4S2PPh2. The compounds were investigated by multinuclear (1H, 13C, 31P, 77Se) NMR and infrared spectroscopy. The crystal and molecular structures of 1, 3, 4 and 6 were determined by single-crystal X-ray diffraction. In compounds 3, 4 and 6 the N(1) atom is intramolecularly coordinated to the selenium center, resulting in a T-shaped geometry (hypervalent 10-Se-3 species). The dithiophosphorus ligands act as anisobidentate in 1 and monodentate in 3, 4 and 6. Supramolecular architectures based on intermolecular S?H and N?H contacts between molecular units are formed in the hypervalent derivatives 3 and 4, while in the compounds 1 and 6 the molecules are associated into polymeric chains through either Se?S or O?H contacts, with no further inter-chain interactions. 相似文献