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1.
A Bi(OTf)(3)/Cu(CH(3)CN)(4)PF(6) system efficiently promoted intermolecular 1:1 hydroamination of 1,3-dienes with various carbamates, sulfonamides, and carboxamides to afford allylic amines in good yield (up to 96%). Reaction proceeded with 0.5-10 mol % catalyst loading at 25-100 degrees C (generally at 50 degrees C) in 1,4-dioxane within 24 h. The Bi(OTf)(3)/Cu(CH(3)CN)(4)PF(6) system constitutes a new entry into series of intermolecular hydroamination catalysis. Mechanistic studies and the postulated reaction mechanism are also discussed.  相似文献   

2.
Dicopper(I) complexes {Cu2(bpnp)(CH3CN)4}(PF6)2] ( 2 ), [{Cu2(bpnp)(CH3CN)4}(BAr4F)2] ( 3 ) and [Cu2(bpnp)Cl2] ( 4 ) were prepared from the complexation of [Cu(CH3CN)4](PF6) with 2,7‐bis(2‐pyridyl)‐1,8‐naphthyridine (bpnp) followed by anion metathesis and treatment of chloride sequentially. The X‐ray structural analysis of 4 indicates the molecule to have a twofold axis passing through the Cu2Cl2 core, which has the shape of a butterfly, and that the Cu atom is tetrahedrally coordinated with in a Cl2N2 donor set. In preliminary experiments 2 was found to be an effective catalyst in the coupling/cyclization of 2‐bromobenzoic acids with amidines, providing the corresponding quinazolinones in good yields. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

3.
Structure and Properties of the Methyltetrafluorophosphate Anion, [CH3PF5] Methyltetrafluorphosphorane reacts with the fluorides NaF, KF, CsF, and (CH3)4NF with formation of the corresponding methylpentafluorophosphates. In case of the K and Cs salts K[CH3PF5] · CH3CN and Cs[CH3PF5] · CH3CN, respectively, are formed using acetonitrile as solvent. The salts are characterized by NMR, IR and Raman spectroscopy. The vibrational frequencies are compared with ab initio calculated data (RHF/6‐31+G*). The RHF/6‐31+G* calculation yields for the almost octahedral anion bond distances of d(PFeq) = 163.7 pm, d(PFax) = 162.0 pm, and d(PC) = 184.8 pm.  相似文献   

4.
Ethylene complexes [OsH(η2‐CH2=CH2)L4]Y ( 1 , 2 ) [L = PPh(OEt)2, P(OEt)3; Y = OTf, BPh4] were prepared by reacting the dihydride OsH2L4 first with methyl triflate CH3OTf and then with ethylene (1 atm). Alternatively, the compound [OsH(η2‐CH2=CH2){PPh(OEt)2}4]OTf was prepared by allowing the dinitrogen derivative [OsH(N2){PPh(OEt)2}4]OTf to react with ethylene. Acrylonitrile CH2=C(H)CN reacts with OsH(OTf)L4 [L = P(OEt)3] to give the complex [OsH{κ1‐NCC(H)=CH2}{P(OEt)3}4]BPh4 ( 3 ). The complexes were characterized spectroscopically (IR and 1H, 13C, 31P NMR) and by X‐ray crystal structure determination of the [OsH(η2‐CH2=CH2){PPh(OEt)2}4]BPh4 derivative.  相似文献   

5.
[LCRP((PhP)2C2H4)][OTf] ( 4 a,b [OTf]) and [LCiPrP(PPh2)2][OTf] ( 5 b [OTf]) were prepared from the reaction of imidazoliumyl‐substituted dipyrazolylphosphane triflate salts [LCRP(pyr)2][OTf] ( 3 a,b [OTf]; a : R=Me, b =iPr; LCR=1,3‐dialkyl‐4,5‐dimethylimidazol‐2‐yl; pyr=3,5‐dimethylpyrazol‐1‐yl) with the secondary phosphanes PhP(H)C2H4P(H)Ph) and Ph2PH. A stepwise double P?N/P?P bond metathesis to catena‐tetraphosphane‐2,3‐diium triflate salt [(Ph2P)2(LCMeP)2][OTf]2 ( 7 a [OTf]2) is observed when reacting 3 a [OTf] with diphosphane P2Ph4. The coordination ability of 5 b [OTf] was probed with selected coinage metal salts [Cu(CH3CN)4]OTf, AgOTf and AuCl(tht) (tht=tetrahydrothiophene). For AuCl(tht), the helical complex [{(Ph2PPLCiPr)Au}4][OTf]4 ( 9 [OTf]4) was unexpectedly formed as a result of a chloride‐induced P?P bond cleavage. The weakly coordinating triflate anion enables the formation of the expected copper(I) and silver(I) complexes [( 5 b )M(CH3CN)3][OTf]2 (M=Cu, Ag) ( 10 [OTf]2, 11 [OTf]2).  相似文献   

6.
The reaction of [(η5‐L3)Ru(PPh3)2Cl], where; L3 = C9H7 ( 1 ), C5Me5 (Cp*) ( 2 ) with acetonitrile in the presence of [NH4][PF6] yielded cationic complexes [(η5‐L3)Ru(PPh3)2(CH3CN)][PF6]; L3= C9H7 ([3]PF6) and L3 = C5Me5 ([4]PF6), respectively. Complexes [3]PF6 and [4]PF6 reacts with some polypyridyl ligands viz, 2,3‐bis (α‐pyridyl) pyrazine (bpp), 2,3‐bis (α‐pyridyl) quinoxaline (bpq) yielding the complexes of the formulation [(η5‐L3)Ru(PPh3)(L2)]PF6 where; L3 = C9H7, L2 = bpp, ([5]PF6), L3 = C9H7, L2 = bpq, ([6]PF6); L3 = C5Me5, L2 = bpp, ([7]PF6) and bpq, ([8]PF6), respectively. However reaction of [(η5‐C9H7)Ru(PPh3)2(CH3CN)][PF6] ([3]PF6) with the sterically demanding polypyridyl ligands, viz. 2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine (tptz) or tetra‐2‐pyridyl‐1,4‐pyrazine (tppz) leads to the formation of unexpected complexes [Ru(PPh3)2(L2)(CH3CN)][PF6]2; L2 = tppz ([9](PF6)2), tptz ([11](PF6)2) and [Ru(PPh3)2(L2)Cl][PF6]; L2 = tppz ([10]PF6), tptz ([12]PF6). The complexes were isolated as their hexafluorophosphate salts. They have been characterized on the basis of micro analytical and spectroscopic data. The crystal structures of the representative complexes were established by X‐ray crystallography.  相似文献   

7.
The lithium tetrakis(methimazolyl)borate, Li[Bmt4], is accessible from the reaction of Li[BH4] with four equivalents of methimazole. The crystal structure of Li[Bmt4] supported by four water molecules is described. Reaction of Li[Bmt4] with [Ru(p‐cymene)Cl2]2 and subsequent treatment with NH4PF6 in CH3CN results in the formation of the complex [Ru(p‐cymene)(Bmt4)][PF6]. In addition, we report the result of the X‐ray structure analysis of the chiral Ru complex [Ru(p‐cymene)(Bmt4)][PF6].  相似文献   

8.
The heterometallic complexes trans ‐[Cp(dppe)FeNCRu(o ‐bpy)CNFe(dppe)Cp][PF6]n ( 1 [PF6]n , n =2, 3, 4; o ‐bpy=1,2‐bis(2,2′‐bipyridyl‐6‐yl)ethane, dppe=1,2‐bis(diphenylphosphino)ethane, Cp=1,3‐cyclopentadiene) in three distinct states have been synthesized and fully characterized. 1 3+[PF6]3 and 1 4+[PF6]4 are the one‐ and two‐electron oxidation products of 1 2+[PF6]2, respectively. The investigated results suggest that 1 [PF6]3 is a Class II mixed valence compound. 1 [PF6]4 after a thermal treatment at 400 K shows an unusually delocalized mixed valence state of [FeIII‐NC‐RuIII‐CN‐FeII], which is induced by electron transfer from the central RuII to the terminal FeIII in 1 [PF6]4, which was confirmed by IR spectroscopy, magnetic data, and EPR and Mössbauer spectroscopy.  相似文献   

9.
The reaction of 2‐(aminomethyl)aniline with 2 equivalents of PPh2Cl in the presence of Et3N, proceeds in CH2Cl2 to give N,N′‐bis(diphenylphosphino)‐2‐(aminomethyl)aniline 1 in good yield. Oxidation of 1 with aqueous H2O2, elemental sulfur or gray selenium gave the corresponding oxide, sulfide and selenide dichalcogenides [Ph2P(E)NHC6H4CH2NHP(E)Ph2] (E: O, 2a; S, 2b; Se, 2c), respectively. The reaction of [Ph2PNHC6H4CH2NHPPh2] with PdCl2(cod), PtCl2(cod) and [Cu(MeCN)4]PF6 gave the corresponding chelate complexes, PdCl21, PtCl21 and [Cu(1)2]PF6. The new compounds were fully characterized by NMR, IR spectroscopy and elemental analysis. The catalytic activity of the Pd(II) complex was tested in the Suzuki coupling and Heck reactions. The Pd(II) complex catalyzes the Suzuki coupling and Heck reaction, affording biphenyls and stilbenes respectively, in good yields. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

10.
Understanding the effects of intermolecular interactions on metal‐to‐metal charge transfer (MMCT) is crucial to develop molecular devices by grafting MMCT‐based molecular arrays. Herein, we report a series of solvent‐free {Fe2Co2} compounds sharing the same cationic tetranuclear {[Fe(PzTp)(CN)3]2[Co(dpq)2]2}2+ (PzTp?=tetrakis(pyrazolyl)borate, dpq=dipyrido[3,2‐d:2′,3′‐f]quinoxaline) square units but having anions with different size, including BF4?, PF6?, OTf?, and [Fe(PzTp)(CN)3]?. Intermolecular π???π interactions between dpq ligands, which coordinate to cobalt ions in the {[Fe(PzTp)(CN)3]2[Co(dpq)2]2}2+ units, can be modulated by introducing different counterions, regulating the distortion of the CoN6 octahedron and ligand field around the cobalt ions. This change results in different MMCT behavior. Computational analyzes reveal the substantial role of the intermolecular interactions tuned by the presence of different counteranions on the MMCT behavior.  相似文献   

11.
The reactions of alkyn‐1‐yl(vinyl)silanes R2Si[C?C‐Si(H)Me2]CH?CH2 [R = Me (1a), Ph (1b)], Me2Si[C?C‐Si(Br)Me2]CH?CH2 (2a), and of alkyn‐1‐yl(allyl)silanes R2Si[C?C‐Si(H)Me2]CH2CH?CH2 (R = Me (3a), R = Ph (3b)] with 9‐borabicyclo[3.3.1]nonane in a 1:1 ratio afford in high yield the 1‐silacyclopent‐2‐ene derivatives 4a, b and 5a, and the 1‐silacyclohex‐2‐ene derivatives 6a, b, respectively, all of which bear a functionally substituted silyl group in 2‐position and the boryl group in 3‐position. This is the result of selective intermolecular 1,2‐hydroboration of the vinyl or allyl group, followed by intramolecular 1,1‐organoboration of the alkynyl group. In the cases of 4a, b, potential electron‐deficient Si? H? B bridges are absent or extremely weak, whereas in 6a,b the existence of Si? H? B bridges is evident from the NMR spectroscopic data (1H, 11B, 13C and 29Si NMR). The molecular structure of 4b was determined by X‐ray analysis. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

12.
The treatment of [AuCl(SMe2)] with an equimolar amount of NaO5NCS2 (O5NCS2=(aza‐[18]crown‐6)dithiocarbamate) in CH3CN gave [Au2(O5NCS2)2] ? 2 CH3CN ( 2? 2 CH3CN), and its crystal structure displays a dinuclear gold(I)‐azacrown ether ring and an intermolecular gold(I) ??? gold(I) contact of 2.8355(3) Å in crystal lattices. It is noted that two other single crystals of 2 ?tert‐butylbenzene?H2O and 2? 0.5 m‐xylene can be successfully obtained from a single‐crystal‐to‐single‐crystal (SCSC) transformation process by immersing single crystals of 2? 2 CH3CN in the respective solvents, and both also show intermolecular gold(I) ??? gold(I) contacts of 2.9420(5) and 2.890(2)–2.902(2) Å, respectively. Significantly, the emissions of all three 2 ?solvates are well correlated with their respective intermolecular gold(I) ??? gold(I) contacts, where such contacts increase with 2? 2 CH3CN (2.8355(3) Å)< 2? 0.5 m‐xylene (2.890(2)–2.902(2) Å)< 2? tert‐butylbenzene?H2O (2.9420(5) Å), and their emission energies increase with 2? 2 CH3CN (602 nm)< 2? 0.5 m‐xylene (583 nm)< 2? tert‐butylbenzene?H2O (546 nm) as well. In this regard, we further examine the solvochromic luminescence for some other aromatics, and finally their emissions are within 546–602 nm. Obviously, the above results are mostly ascribed to the occurrence of intermolecular gold(I) ??? gold(I) contacts in 2 ?solvates, which are induced by the presence of various solvates in the solid state, as a key role to be responsible for their solvochromic luminescence.  相似文献   

13.
C6F5I(CN)2 and x‐FC6H4I(CN)2 (x = 2, 3, 4) were isolated from reactions of the corresponding aryliodine difluorides ArIF2 and a stoichiometric excess of Me3SiCN in CCl3F (0 °C) or CH2Cl2 (20 °C), respectively. In addition, x‐FC6H4I(CN)2 compounds were synthesized in good yields on alternative routes, namely from 3‐ or 4‐FC6H4I(OC(O)CH3)2 or 4‐FC6H4I(OC(O)CF3)2 or from 4‐FC6H4IO and Me3SiCN in CH2Cl2 at 20 °C. In the 1 : 1 reaction of C6F5IF2 and Me3SiCN a lower temperature was necessary to suppress partial disubstitution and to obtain the first example of a new type of aryliodine(III) cyanide compounds, C6F5I(CN)F. 4‐FC6H4I(CN)F could be isolated from the equimolar reaction of 4‐FC6H4IF2 and Me3SiCN in CH2Cl2 even at 20 °C. The new products were characterized by multi‐NMR and Raman spectroscopy. The molecular structures of C6F5I(CN)2, 3‐ and 4‐FC6H4I(CN)2, C6F5I(CN)F, and 4‐FC6H4I(CN)F are discussed and compared with that of C6F5IF2. The reactivity of C6F5I(CN)F towards fluoride acceptors EFn (BF3, AsF5) and RxEX?x (C6F5SiF3, C6H5SiF3, C6H5PF4, Me3SiCl, Me3SiC6F5) were investigated and showed differing reaction patterns (fluoride abstraction, aryl transfer, chloride transfer). Besides the molecular entities C6F5I(CN)F and C6F5I(CN)Cl, the corresponding iodonium salts [C6F5(CN)I][BF4] and [C6F5(CN)I][AsF6] were isolated. The thermal stability of ArI(CN)2 and ArI(CN)F, neat and in solution, as well as the reactivity of 4‐FC6H4I(CN)2 towards the Lewis acid BF3 are reported.  相似文献   

14.
The reactions of thiophene‐2‐(N‐diphenylphosphino)methylamine, Ph2PNHCH2‐C4H3S, 1 and thiophene‐2‐[N,N‐bis(diphenylphosphino)methylamine], (Ph2P)2NCH2‐C4H3S, 2, with MCl2(cod) (M = Pd, Pt; cod = 1,5‐cyclooctadiene) or [Cu(CH3CN)4]PF6 yields the new complexes [M(Ph2PNHCH2‐C4H3S)2Cl2], M = Pd 1a, Pt 1b, [Cu(Ph2PNHCH2‐C4H3S)4]PF6, 1c, and [M(Ph2P)2NCH2‐C4H3S)Cl2], M = Pd 2a, Pt 2b, {Cu[(Ph2P)2NCH2‐C4H3S]2}PF6, 2c, respectively. The new compounds were isolated as analytically pure crystalline solids and characterized by 31P‐, 13C‐, 1H‐NMR and IR spectroscopy and elemental analysis. Furthermore, the solid‐state molecular structures of representative palladium and platinum complexes of bis(phosphine)amine, 2a and 2b, respectively, were determined using single crystal X‐ray diffraction analysis. The palladium complexes were tested as potential catalysts in the Heck and Suzuki cross‐coupling reactions. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

15.
Four aluminum alkyl compounds, [CH{(CH3)CN‐2,4,6‐MeC6H2}2AlMe2] ( 1 ), [CH{(CH3)CN‐2,4,6‐MeC6H2}2AlEt2] ( 2 ), [CH{(CH3)CN‐2‐iPrC6H4}2AlMe2] ( 3 ), and [CH{(CH3)CN‐2‐iPrC6H4}2AlEt2] ( 4 ), bearing β‐diketiminate ligands [CH{(Me)CN‐2,4,6‐MeC6H2}]2 (L1H) and [CH{(Me)CN‐2‐iPrC6H4}]2 (L2H) were obtained from the reactions of trimethylaluminum, triethylaluminum with the corresponding β‐diketiminate, respectively. All compounds were characterized by 1H NMR and 13C NMR spectroscopy, single‐crystal X‐ray structural analysis, and elemental analysis. Compounds 1 – 4 were found to catalyze the ring‐opening polymerization (ROP) of ε‐caprolactone (ε‐CL) with good activity.  相似文献   

16.
An efficient and versatile methodology for the preparation of valuable triazolyl aminoacyl (peptidyl) penicillins is described. Solid-phase Cu(I)-catalyzed Hüisgen 1,3-dipolar cycloaddition was used as the key step showing general applicability and excellent regioselectivity either with CuI or [Cu(CH3CN)4]PF6 as Cu(I) source.  相似文献   

17.
A series of half‐sandwich rhodium‐based metallamacrocycles with tetra‐ and hexanuclearities have been synthesized. They are assembled by linking the deprotonated 2,4‐diacetyl‐5‐hydroxy‐5‐methyl‐3‐(3‐pyridinyl)cyclohexanone (HL) ligand in the presence of counteranions. When the counteranion was the tetrahedral BF4? ion, tetranuclear metallamacrocycle [(Cp*RhL)4][BF4]4 ( 1 d ) was formed. However, the larger OTf?, PF6?, and SbF6? counterions favored the formation of hexanuclear metallamacrocycles [(Cp*RhL)6?2OTf][OTf]4 ( 1 a ), [(Cp*RhL)6?2PF6][PF6]4 ( 1 b ), and [(Cp*RhL)6?2SbF6][SbF6]4 ? 6CH3CN ( 1 c ) when the reactions were performed under the same conditions. Single‐crystal X‐ray analysis indicated that, in the solid state, two counteranions were encapsulated in each belt‐like host molecule of hexanuclear metallamacrocycles 1 a , b , and c . Based on the results of 1H NMR analysis in methanol, the nuclearities of 1 a – c and the two encapsulated anions in each molecular cavity were maintained in solution. In addition, tetranuclear metallamacrocycle 1 d was converted into the hexanuclear metallamacrocycles 1 a′ , b , and c after addition of the appropriate anion as its [NBu4]+ salt. The compound 1 a′ was characterized by single‐crystal X‐ray diffraction to have the formula [(Cp*RhL)6?2OTf][BF4]4 ? 2M eOH ? 2H2O. From the interconversion of the hexanuclear metallamacrocycles, we have concluded that the hexanuclear belt‐like host in 1 a – c has an clear selectivity for larger anions, in the sequence SbF6?≈PF6?>OTf?>BF4?>Cl?.  相似文献   

18.
Mono‐ and multinuclear complexes of ruthenium and [n]cycloparaphenylene (CPP, n=5 and 6) were synthesized in excellent yields through ligand exchange of the cationic complex [(Cp)Ru(CH3CN)3](PF6) with CPP. In the multinuclear complexes, ruthenium selectively coordinated to alternate paraphenylene units to give bis‐ and tris‐coordinated Ru complexes for [5] and [6]CPPs, respectively. Single‐crystal X‐ray analysis revealed the Ru was coordinated with η6‐hapticity on the convex surface of CPP.  相似文献   

19.
To investigate how the central metalloligand geometry influences distant or vicinal metal‐to‐metal charge‐transfer (MMCT) properties of polynuclear complexes, cis‐ and trans‐isomeric heterotrimetallic complexes, and their one‐ and two‐electron oxidation products, cis/trans‐ [Cp(dppe)FeIINCRuII(phen)2CN‐FeII(dppe)Cp][PF6]2 (cis/trans‐ 1 [PF6]2), cis/trans‐[Cp(dppe)FeIINCRuII(phen)2CNFeIII‐(dppe)Cp][PF6]3 (cis/trans‐ 1 [PF6]3) and cis/trans‐[Cp(dppe)FeIIINCRuII(phen)2CN‐FeIII(dppe)Cp][PF6]4 (cis/trans‐ 1 [PF6]4) have been synthesized and characterized. Electrochemical measurements show the presence of electronic interactions between the two external FeII atoms of the cis‐ and trans‐isomeric complexes cis/trans‐ 1 [PF6]2. The electronic properties of all these complexes were studied and compared by spectroscopic techniques and TDDFT//DFT calculations. As expected, both mixed valence complexes cis/trans‐ 1 [PF6]3 exhibited different strong absorption signals in the NIR region, which should mainly be attributed to a transition from an MO that is delocalized over the RuII‐CN‐FeII subunit to a FeIII d orbital with some contributions from the co‐ligands. Moreover, the NIR transition energy in trans‐ 1 [PF6]3 is lower than that in cis‐ 1 [PF6]3, which is related to the symmetry of their molecular orbitals on the basis of the molecular orbital analysis. Also, the electronic spectra of the two‐electron oxidized complexes show that trans‐ 1 [PF6]4 possesses lower vicinal RuII→FeIII MMCT transition energy than cis‐ 1 [PF6]4. Moreover, the assignment of MMCT transition of the oxidized products and the differences of the electronic properties between the cis and trans complexes can be well rationalized using TDDFT//DFT calculations.  相似文献   

20.
Ion‐like ethylzinc(II) compounds with weakly coordinating aluminates [Al(ORF)4]? and [(RFO)3Al‐F‐Al(ORF)3]? (RF=C(CF3)3) were synthesized in a one‐pot reaction and fully characterized by single‐crystal X‐ray diffraction, NMR and vibrational spectroscopy, and by quantum chemical calculations. The catalytic activity of ion‐like Et‐Zn[Al(ORF)4] in intermolecular hydroamination and in the unusual double hydroamination of anilines and alkynes was investigated. Favorable performance was also found in comparison to the Et2Zn/ [PhNMe2H]+[B(C6F5)4]? system generated in situ at lower catalyst loadings of 2.5 mol %.  相似文献   

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