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1.
Rate coefficients have been measured at 298 ± 4 K and 1000 mbar total pressure for the reactions of OH with a series of symmetrical acetals (R O CH2 O R, R = C1 to C4) using a relative kinetic technique. The investigations have been performed in a laboratory photoreactor and also in the large outdoor EUPHORE simulation chamber facility in Valencia, Spain. The following rate coefficients (in units of 10−11 cm3 molecule−1 s−1) have been obtained: dimethoxy methane (R = CH3), 0.49 ± 0.02; diethoxy methane (R = CH3CH2), 1.84 ± 0.18; di‐n‐propoxy methane (R = CH3CH2CH2), 2.63 ± 0.49; di‐iso‐propoxy methane (R = (CH3)2CH), 3.93 ± 0.48; di‐n‐butoxy methane (R = CH3CH2CH2CH2), 3.47 ± 0.42; di‐iso‐butoxy methane (R = (CH3)2CHCH2), 3.68 ± 0.57; di‐sec‐butoxy methane (R = CH3CH2C(CH3)H), 4.68 ± 0.05. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 797–803, 1999  相似文献   

2.
Four new mixed‐ring zirconium completes, [CH2 = CH(CH2)n ‐C5H4](RC5H4)ZrCl2 [n = l, R = CH3OCH2CH2(3); n = 2, R = CH3OCH2CH2 (4); n = 2, R=Me3Si (5); n = 2, R = allyl (6)], have been prepared by the reaction of CH2 = CH(CH2)n C5H4ZrCl3, DME[n = l (1); n = 2 (2)] with RC5H4Li. When activated with methylaluminoxane (MAO), the catalytic activities of the above complexes in ethylene polymerization were tested. Complexes 5 and 6 show high activities similar to Cp2ZrCl2. Introduction of methoxyethyl group into Cp‐ligand dramatically decreases the catalytic activities of complexes 3 and 4, which can be overcome by increasing the amount of MAO. For complex 5, the dependence of activity and molecular weight (Mη) on the Al/Zr ratio, the polymerization time (tP), polymerization temperature (TP) and the polymerization solvent volume (V) was investigated.  相似文献   

3.
Two unsymmetric meso‐tetraferrocenyl‐containing porphyrins of general formula Fc3(FcCOR)Por (Fc=ferrocenyl, R=CH3 or (CH2)5Br, Por=porphyrin) were prepared and characterized by a variety of spectroscopic methods, whereas their redox properties were investigated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) approaches. The mixed‐valence [Fc3(FcCOR)Por]n+ (n=1,3) were investigated using spectroelectrochemical as well as chemical oxidation methods and corroborated with density functional theory (DFT) calculations. Inter‐valence charge‐transfer (IVCT) transitions in [Fc3(FcCOR)Por]+ were analyzed, and the resulting data matched closely previously reported complexes and were assigned as Robin–Day class II mixed‐valence compounds. Self‐assembled monolayers (SAMs) of a thioacetyl derivative (Fc3(FcCO(CH2)5SCOCH3)Por) were also prepared and characterized. Photoelectrochemical properties of SAMs in different electrolyte systems were investigated by electrochemical techniques and photocurrent generation experiments, showing that the choice of electrolyte is critical for efficiency of redox‐active SAMs.  相似文献   

4.
The synthesis of trimethylene-bridged carboxylate-substituted tetraorganodistannoxanes {[Me3SiCH2(RCOO)Sn(CH2)3Sn(OOCR)CH2SiMe3]O} n (1, R = Ph; 2, R = 2,4-Me2C6H3) is reported. Depending on the structure of R, in the solid state these compounds are either dimers (1, n = 2, cis-isomer) with a ladder-type structure or tetramers (2, n = 4) with a double ladder-type structure.  相似文献   

5.
Reactions of PhAsCl2 with BrMg(CH2)nMgBr (n = 4 or 5) in THF gave phenylarsacycloalkanes as colourless oily liquids which could be distilled under vacuum. Treatment of PhAs(CH2)n­with MCl2(RCN)2 (M = Pd or Pt; R = Ph­or Me) afforded mononuclear complexes, [MCl2{PhAs(CH2)n}2]. Reactions with [Pt2Cl2(μ‐Cl)2(PEt3)2] gave mixed‐ligand complexes, [PtCl2(PEt3){PhAs(CH2)n]. The palladium complexes adopt a trans geometry whereas the platinum complexes exist in a cis configuration. The crystal and molecular structure of [PdCl2(PhAsCH2CH2CH2CH2CH2)2] was determined by X‐ray diffraction methods. The molecule consists of a square‐planar palladium atom with trans chlorides and trans arsa ligands. The six‐membered ‘AsC5′ ring adopts a chair conformation. Copyright © 1999 John Wiley & Sons, Ltd.  相似文献   

6.
New Group 3 metal complexes of the type [LM(CH2SiMe3)2(THF)n] supported by tridentate phosphido‐diphosphine ligands [(o‐C6H4PR2) 2 PH; L1‐H : R = iPr; L2‐H : R = Ph] have been synthesized by reaction of L1‐H and L2‐H with [M(CH2SiMe3)3(THF)2)] (M = Y and Sc). All the new complexes [(o‐C6H4PR2) 2 PM(CH2SiMe3)2(THF)n] [M = Y, R = iPr (1), R = Ph (2); M = Sc, R = iPr (3), R = Ph (4)] were studied as initiators for the ring opening polymerization of lactide. The yttrium complexes ( 1 and 2 ) exhibited high activity and good polymerization control, shown by the linear fits in the plot of number‐averaged molecular weight (Mn) versus the percentage conversion and versus the monomer/initiator ratio and by the low polydispersity index values. Interestingly, very good molar‐mass control was observed even when L ‐Lactide was polymerized in the absence of solvent at 130 °C. A good molar‐mass control but lower activities were observed in the polymerization reaction of lactide promoted by the analogous scandium complexes 3 and 4 . © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1374–1382, 2010  相似文献   

7.
Sulfur‐substituted methylmercury compounds [Hg(CH2SR)2]( 1a, R = Me; 1b, R = Ph ) react with aluminium amalgam in refluxing toluene with transmetallation to give homoleptic tris(thiomethyl)aluminium complexes [Al(CH2SR)3]( 2a, R = Me; 2b, R = Ph ) (degree of conversion: >80%, isolated yields: 2a 63%, 2b 41%). Their identities were confirmed by NMR spectros‐copy (1H, 13C) and X‐ray crystal structure analyses. In crystals of compound 2a the aluminium atoms possess a trigonal‐bipyramidal arrangement with the coordination polyhedron defined by three carbon and two sulfur atoms. Two of the three CH2SMe ligands are bridging ligands (μ‐η2; 1kC:2kS), the third one is terminal bound (η1; kC). The structure is polymeric. Crystals are threaded by helical chains built up of six‐membered Al2C2S2 rings. Crystals of 2b are built up of centrosymmetrical dimers with six‐membered Al2C2S2 rings having bridging CH2SPh ligands (μ‐η2; 1kC:2kS). On each Al atom two terminal (η1; kC)CH2SPh ligands are bound. They exhibit quite different Al‐C‐S angles (116.7(4) and 106.5(3)?). Similar values (114.32115.7? and 109.52109.9?) were found in ab initio calculations of model compounds [{Al(CH2SR)3}2]( 3a, R=H; 3b, R=Me; 3c, R=CH=CH2 ). A conformational energy diagram for rotation of one of the terminal CH2SH ligand in the parent compound 3a around the Al‐C bond is discussed in terms of repulsive interactions of lone electron pairs of sulfur atoms.  相似文献   

8.
Connecting two discotic mesogens via a spacer not only stabilizes the columnar mesophase but also leads to the formation of glass columnar phase, and therefore improves the physical properties of discotic liquid crystals as organic semiconductor. Here, we report the synthesis of eight diacetylene-bridged triphenylene discotic liquid crystal dimers, [C18H6(OCnH2n+1)4(OMe)O2C-C8H16-C≡≡ C-]2, 3(n), (n = 4-8), [C18H6(OC6H13)5O2C-C8H16-C≡≡ C-]2, 6 and [C18H6(OC6H13)5O-(CH2)m-C≡≡ C-]2, 8(m), (m = 1, 3) by Eglinto...  相似文献   

9.
Water‐soluble palladium complexes cis‐[Pd(L)(OAc)2] ( 1–8 ) (L represents a diphosphine ligands of the general formula CH2(CH2PR2)2, where for a : R ? (CH2)6OH; b–g : R ? (CH2)nP(O)(OEt)2, n = 2–6 and n = 8; h : R ? (CH2)3NH2) have been employed, after activation with a large excess of HBF4, for emulsion polymerization of alkenes (propene, butene, and their equimolar mixtures) with carbon monoxide. Aliphatic polyketone lattices with a high solid content (21%), high molecular weight (6.3 × 104 g mol?1), and narrow polydispersities (Mw/Mn ≈ 2) were isolated. The catalytic activity of the dicationic palladium (II) based catalysts, C1–C8 is highly dependent on the length of the alkyl chain of the ligand. Catalyst 3 proved to be highly active for propene/CO copolymers, whereas 6 is active for butene/CO and propene/CO‐butene/CO systems. The presence of methyl β‐cyclodextrin, as a phase‐transfer agent, and undecenoic acid, as an emulsifier, increase the molar mass and the stability of the polyketones and finally the activity of the catalyst. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6715–6725, 2009  相似文献   

10.
Building upon previous studies on the synthesis of bis(sigma)borate and agostic complexes of ruthenium, the chemistry of nido‐[(Cp*Ru)2B3H9] ( 1 ) with other ligand systems was explored. In this regard, mild thermolysis of nido‐ 1 with 2‐mercaptobenzothiazole (2‐mbzt), 2‐mercaptobenzoxazole (2‐mbzo) and 2‐mercaptobenzimidazole (2‐mbzi) ligands were performed which led to the isolation of bis(sigma)borate complexes [Cp*RuBH3L] ( 2 a – c ) and β‐agostic complexes [Cp*RuBH2L2] ( 3 a – c ; 2 a , 3 a : L=C7H4NS2; 2 b , 3 b : L=C7H4NSO; 2 c , 3 c : L=C7H5N2S). Further, the chemistry of these novel complexes towards various diphosphine ligands was investigated. Room temperature treatment of 3 a with [PPh2(CH2)nPPh2] (n=1–3) yielded [Cp*Ru(PPh2(CH2)nPPh2)‐BH2(L2)] ( 4 a – c ; 4 a : n=1; 4 b : n=2; 4 c : n=3; L=C7H4NS2). Mild thermolysis of 2 a with [PPh2(CH2)nPPh2] (n=1–3) led to the isolation of [Cp*Ru(PPh2(CH2)nPPh2)(L)] (L=C7H4NS2 5 a – c ; 5 a : n=1; 5 b : n=2; 5 c : n=3). Treatment of 4 a with terminal alkynes causes a hydroboration reaction to generate vinylborane complexes [Cp*Ru(R?C?CH2)BH(L2)] ( 6 and 7 ; 6 : R=Ph; 7 : R=COOCH3; L=C7H4NS2). Complexes 6 and 7 can also be viewed as η‐alkene complexes of ruthenium that feature a dative bond to the ruthenium centre from the vinylinic double bond. In addition, DFT computations were performed to shed light on the bonding and electronic structures of the new compounds.  相似文献   

11.
CO2 fixation and transformation by metal complexes continuously receive attention from the viewpoint of carbon resources and environmental concerns. We found that the dinuclear copper(II) cryptate [Cu2L1](ClO4)4 ( 1 ; L1=N[(CH2)2NHCH2(m‐C6H4)CH2NH‐(CH2)2]3N) can easily take up atmospheric CO2 even under weakly acidic conditions at room temperature and convert it from bicarbonate into carbonate monoesters in alcohol solution. The compounds [Cu2L1O2COH)](ClO4)3 ( 2 ), [Cu2L1(μ‐O2COR)](ClO4)3 ( 3 : R=CH3; 4 : R=C2H5; 5 : R=C3H7; 6 : R=C4H9; 7 : R=C5H11; 8 : R=CH2CH2OH), [Cu2L1O2CCH3)](ClO4)3 ( 9 ), and [Cu2L1(OH2)(NO3)](NO3)3 ( 10 ) were characterized by IR spectroscopy and ESI‐MS. The crystal structures of 2 – 6 and 10 were studied by single‐crystal X‐ray diffraction analysis. On the basis of the crystal structures, solution studies, and DFT calculations, a possible mechanism for CO2 fixation and transformation is given.  相似文献   

12.
By reactions of Mo2(O2CPrn)X2(PPh3)2 (X = Cl, 1 ; X = Br, 2 ) with Ph2PCH2CH2P(Ph)CH2CH2PPh2 (etp) in CH2X2, the quadruply bonded complexes containing bridging butyrate and tridentate phosphine ligands of the type Mo2(O2CPrn)X33‐etp) (X = Cl, 3 ; X = Br, 4 ) were prepared. Their UV‐vis and31P{1H}‐NMR spectra have been recorded and the structures of 1 and 2 have been determined by X‐ray crystallography. Crystal data for 1 : space group P21/c, a = 9.708 (2)Å, b = 18.491 (4)Å, c= 12.688 (3)Å, β = 110.76 (3)°, V = 2130 Å3, Z = 2, with final residuals R = 0.0441 and Rw = 0.0519. Crystal data for 2 : space group P21/c, a = 9.737 (1)Å, b = 18.632(1)Å, c = 12.680(1)Å, β= 110.27 (1)°,V = 2158.2 (3) Å3, Z = 2, with final residuals R = 0.0322 and Rw = 0.0481. The δ → δ* transition energies, 31P{1H}‐NMR chemical shifts and the coupling constants are dependent on the natures of the halogen atoms and the carboxylate ligands. The through metal‐metal couplings |3JP‐Mo‐Mo‐P| for complexes of the type Mo2(O2CR)X33‐P3), which contain η3‐polydentate phosphine ligands are about 20 ± 2 Hz.  相似文献   

13.
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   

14.
Reactions of one or two equiv. of cyclohexyl isocyanide in THF at room temperature with Mo?Mo triply bonded complexes [Mo(CO)2(η5‐C5H4R)]2 (R=COCH3, CO2CH3) gave the isocyanide coordinated Mo? Mo singly bonded complexes with functionally substituted cyclopentadienyl ligands, [Mo(CO)2(η5‐C5H4R)]2(μη2‐CNC6H11) ( 1a , R=COCH3; 1b , R=CO2CH3) and [Mo(CO)2(η5‐C5H4R)(CNC6H11)]2 ( 2a , R=COCH3; 2b , R=CO2CH3), respectively. Complexes 1a , 1b and 2a , 2b could be more conveniently prepared by thermal decarbonylation of Mo? Mo singly bonded complexes [Mo(CO)3(η5‐C5H4R)]2 (R=COCH3, CO2CH3) in toluene at reflux, followed by treatment of the resulting Mo?Mo triply bonded complexes [Mo(CO)2(η5‐C5H4R)]2 (R=COCH3, CO2CH3) in situ with cyclohexyl isocyanide. While 1a , 1b and 2a , 2b were characterized by elemental analysis and spectroscopy, 1b was further characterized by X‐ray crystallography.  相似文献   

15.
Heterometal‐doped gold clusters are poorly accessible through wet‐chemical approaches and main‐group‐metal‐ or early‐transition‐metal‐doped gold clusters are rare. Compounds [M(AuPMe3)11(AuCl)]3+ (M=Pt, Pd, Ni) ( 1 – 3 ), [Ni(AuPPh3)(8?2n)(AuCl)3(AlCp*)n] (n=1, 2) ( 4, 5 ), and [Mo(AuPMe3)8 (GaCl2)3(GaCl)]+ ( 6 ) were selectively obtained by the transmetalation of [M(M′Cp*)n] (M=Mo, E=Ga, n=6; M=Pt, Pd, Ni, M′=Ga, Al, n=4) with [ClAuPR3] (R=Me, Ph) and characterized by single‐crystal X‐ray diffraction and ESI mass spectrometry. DFT calculations were used to analyze the bonding situation. The transmetalation proved to be a powerful tool for the synthesis of heterometal‐doped gold clusters with a design rule based on the 18 valence electron count for the central metal atom M and in agreement with the unified superatom concept based on the jellium model.  相似文献   

16.
《中国化学会会志》2017,64(1):61-72
The stable tribridged dicopper(I) carboxylate complexes [Cu2(μ‐dppm)2(μ‐O2CR)]BF4 (RCO2 = formate (OFc), m1 ; acetate (OAc), m2 ; benzoate (OBAc), m3 ; o‐toluate (O2TAc), m4 ; p‐toluate (O4TAc), m5 ; 4‐phenylbutyrate (O4PBAc), m6 ; 2‐nitrobenzoate (O2NBAc), m7 ), abbreviated as MM, and neutral dipyridyl compounds (NN; NN = 4,4′‐bipyridine (bpy), 1,2‐bis(4‐pyridyl)ethane (bpa), trans ‐1,2‐bis(4‐pyridyl)ethylene (bpe), 4,4′‐trimethylenedipyridine (tmp)) can form dynamic equilibria in CH2Cl2. From the equilibrium mixtures containing MM and NN with MM/NN = 1:1, nine 2:1 oligomers ([( m1 )2(μ‐bpy)](BF4)2 ( o1a (BF4)2), [( m3 )2(μ‐bpe)](BF4)2 ( o3c (BF4)2), [( m3 )2(μ‐tmp)](BF4)2 ( o3d (BF4)2), [( m4 )2(μ‐bpe)](BF4)2 ( o4c (BF4)2), [( m5 )2(μ‐bpy)](BF4)2 ( o5a (BF4)2), [( m5 )2(μ‐tmp)](BF4)2 ( o5d (BF4)2), [( m6 )2(μ‐bpa)](BF4)2 ( o6b (BF4)2), [( m7 )2(μ‐bpy)](BF4)2 ( o7a (BF4)2), [( m7 )2(μ‐bpa)](BF4)2 ( o7b (BF4)2)), one 2:3 oligomer ([{( m2 )(bpy)}2(μ‐bpy)](BF4)2 ( o2a (BF4)2)), and five 1:1 polymers ([( m2 )(μ‐bpe)] n (BF4 ) n ( p2c (BF4 ) n ), [( m2 )(μ‐tmp)] n (BF4 ) n ( p2d (BF4 ) n ), [( m3 )(μ‐bpy)] n (BF4 ) n ( p3a (BF4 ) n ), [( m3 )(μ‐tmp)] n (BF4 ) n ( p3d (BF4 ) n ), [( m7 )(μ‐tmp)] n (BF4 ) n ( p7d (BF4 ) n )) were obtained as single crystals, and their structures were determined by X‐ray crystallography. Both experimental and theoretical results support the presence of two oligomeric species, [{Cu2(μ‐dppm)2(μ‐O2CR)}2(μ‐NN)]2+ and [{Cu2(μ‐dppm)2(μ‐O2CR)(NN)}2(μ‐NN)]2+), in dynamic equilibrium. The oligomers (such as o3d (BF4)2) can serve as seeds to induce the formation of soluble coordination polymers as crystals (such as p3d (BF4)n ).  相似文献   

17.
《Polyhedron》1988,7(6):449-462
The complexes [ML*(NO)Cl(OR)] {L* = HB(3,5-Me2C3HN2)3; M= Mo, R = CH2CH2X, X = Cl, OMe or OEt; (CH2)nOH, n = 2, 5, 6; M = W, R = CH2CH2X, X = Cl, OMe or OEt; (CH2)nOH, n = 2–6; CH2(CF2)3CH2OH; CHMeCH2CMe2OH} and [ML*(NO)(OR)2] {M = Mo, R = CH2CH2X, X = Cl, OMe or OEt; (CH2)nOH, n = 2–6; M = W,R = CH2CH2X, X= Cl, OMe or OEt; (CH2)nOH, n = 2,4–6; CH2(CF2)3CH2OH} have been prepared from [ML*(NO)Cl2] and the appropriate alcohol in the presence of NEt3 or NaCO3, and have been characterized by IR, 1H NMR and mass spectroscopy.  相似文献   

18.
The tetrameric Cu(β-diketonate) alkoxide complex [Cu(thd)(OCH2CH2OCH3)]4 (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate; 1a ) reacts with the alkaline earth metal alkoxides [M(OCH2CH2OCH3)2] (M = Ca, 2a ; M = Sr, 2b ; M = Ba, 2c ) to yield the heteronuclear compounds [Cu2M(thd)3(OCH2CH2OCH3)3] (M = Ca, 6a ; M = Sr, 6b ). These heterometallic complexes were also obtained in the reaction of 1a and the mixed Ca and Sr complexes of β-diketonate-alkoxide [Mx(thd)y(OCH2CH2OCH3)2x?y] (M = Ca, x = 7, y = 6, 3 ; M = Sr, x = 5, y = 3, 4 ), respectively. In comparison, 1a reacts with the analogous [Ba(thd)(OCH2CH2OCH3)] ( 5a ) to yield a[Ba2Cu2(thd)4(OCH3)4(HOCH2CH2OCH3)2] species ( 8a .) The in situ prepared mixed-ligand Ba Compounds [Ba(thd)OR)] (R = CH2CH2OCH2CH2OCH3, ( 5b ); R = CH2CH2CH2OCH3 ( 5c ) react with the corresponding Cu complexes [Cu(thd)(OR)]n (R = CH2CH2OCH2CH2OCH3), n = 4 ( 1b ); R = CH2CH2OCH2CH2OCH3 ( 8b ); R = CH2CH2CH2OCH3 ( 8c ). However, [Cu(hfd)(OCH2CH2OCH3)]4 (hfd = 1,1,1,5,5,5,-hexafluoroacetylacetonate; 1e ) is converted in the presence of 2a–c to the simple metathesis products [M(hfd)2] (M = Ca, Sr, Ba) and [Cu(OCH2CH2OCH3)2]. Crystalline [Ba2Cu2(hfd)2(thd)2(OCH2CH2CH2OCH3)4(HOCH2CH2CH2OCH3)2] ( 9 ) was isolated from the reaction of 1a with in situ prepared [Ba((hfd)OCH2CH2CH2OCH3)] ( 5d ) in 2-, methoxyethanol. X-Ray crystallographic structure determinations are reported for 6a , 6b , 8b , and 8c .  相似文献   

19.
Herein, we report the syntheses of silicon‐ and tin‐containing open‐chain and eight‐membered‐ring compounds Me2Si(CH2SnMe2X)2 ( 2 , X=Me; 3 , X=Cl; 4 , X=F), CH2(SnMe2CH2I)2 ( 7 ), CH2(SnMe2CH2Cl)2 ( 8 ), cyclo‐Me2Sn(CH2SnMe2CH2)2SiMe2 ( 6 ), cyclo‐(Me2SnCH2)4 ( 9 ), cyclo‐Me(2?n)XnSn(CH2SiMe2CH2)2SnXnMe(2?n) ( 5 , n=0; 10 , n = 1, X= Cl; 11 , n=1, X= F; 12 , n=2, X= Cl), and the chloride and fluoride complexes NEt4[cyclo‐ Me(Cl)Sn(CH2SiMe2CH2)2Sn(Cl)Me?F] ( 13 ), PPh4[cyclo‐Me(Cl)Sn(CH2SiMe2CH2)2Sn(Cl)Me?Cl] ( 14 ), NEt4[cyclo‐Me(F)Sn(CH2SiMe2CH2)2Sn(F)Me?F] ( 15 ), [NEt4]2[cyclo‐Cl2Sn(CH2SiMe2CH2)2SnCl2?2 Cl] ( 16 ), M[Me2Si(CH2Sn(Cl)Me2)2?Cl] ( 17 a , M=PPh4; 17 b , M=NEt4), NEt4[Me2Si(CH2Sn(Cl)Me2)2?F] ( 18 ), NEt4[Me2Si(CH2Sn(F)Me2)2?F] ( 19 ), and PPh4[Me2Si(CH2Sn(Cl)Me2)2?Br] ( 20 ). The compounds were characterised by electrospray mass‐spectrometric, IR and 1H, 13C, 19F, 29Si, and 119Sn NMR spectroscopic analysis, and, except for 15 and 18 , single‐crystal X‐ray diffraction studies.  相似文献   

20.
Some new types of mononuclear derivatives, AlL(1–4)L(1–4)H ( 1a–1d ) of aluminium were synthesized by the reaction of Al(OPri)3 and LH2 [XC(NYOH)CHC(R)OH], X = CH3, Y = (CH2)2, R = CH3(L1H2); X = C6H5, Y = (CH2)2, R = CH3(L2H2); X = CH3, Y = (CH2)3, R = CH3(L3H2); X = C6H5, Y = (CH2)3, R = CH3(L4H2) in 1:2 molar ratio in refluxing benzene. Reactions of AlL(1–4)L(1–4)H with hexamethyldisilazane in 2:1 molar ratio yielded some new ligand bridged heterodinuclear derivatives AlL(1–4)L(1–4)SiMe3 ( 2a – 2d ). All these newly synthesized derivatives were characterized by elemental analysis and molecular weight measurements. Tentative structures were proposed on the basis of IR and NMR spectra (1H, 13C, 27 Al and 29Si) and FAB‐mass studies. Schiff base ligands and their mono‐ and heterodi‐nuclear derivatives with aluminium have been screened for fungicidal activities. These compounds showed significant antifungal activity against Aspergillus niger and A. flavus. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   

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