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1.
Susie Douglas Mary F. Mahon Michael K. Whittlesey 《Journal of organometallic chemistry》2005,690(23):5027-5035
Addition of excesses of N-heterocyclic carbenes (NHCs) IEt2Me2, IiPr2Me2 or ICy (IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene; IiPr2Me2 = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene; ICy = 1,3-dicyclohexylimidazol-2-ylidene) to [HRh(PPh3)4] (1) affords an isomeric mixture of [HRh(NHC)(PPh3)2] (NHC = IEt2Me2 (cis-/trans-2), IiPr2Me2 (cis-/trans-3), ICy (cis-/trans-4) and [HRh(NHC)2(PPh3)] (IEt2Me2(cis-/trans-5), IiPr2Me2 (cis-/trans-6), ICy (cis-/trans-7)). Thermolysis of 1 with the aryl substituted NHC, 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene (IMesH2), affords the bridging hydrido phosphido dimer, [{(PPh3)2Rh}2(μ-H)(μ-PPh2)] (8), which is also the reaction product formed in the absence of carbene. When the rhodium precursor was changed from 1 to [HRh(CO)(PPh3)3] (9) and treated with either IMes (=1,3-dimesitylimidazol-2-ylidene) or ICy, the bis-NHC complexes trans-[HRh(CO)(IMes)2] (10) and trans-[HRh(CO)(ICy)2] (11) were formed. In contrast, the reaction of 9 with IiPr2Me2 gave [HRh(CO)(IiPr2Me2)2] (cis-/trans-12) and the unusual unsymmetrical dimer, [(PPh3)2Rh(μ-CO)2Rh(IiPr2Me2)2] (13). The complexes trans-3, 8, 10 and 13 have been structurally characterised. 相似文献
2.
Victor M. Karpov Vyacheslav E. Platonov Tatjana V. Rybalova Yuri V. Gatilov Makhmut M. Shakirov 《Journal of fluorine chemistry》2006,127(7):936-942
Acetic acid-catalyzed condensation of 2-amino-3-(1-imino-2,2,2-trifluoroethyl)-1,1,4,5,6,7-hexafluoroindene (1b) with acetone and cyclopentanone gives 5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-2,3-dihydro-1,3-diazafluorene (2a) and 5,6,7,8,9,9-hexafluoro-4-trifluoromethyl-2,3-dihydro-1,3-diazafluorene-2-spiro-1′-cyclopentane (3a) together with small amounts of 5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-1,2-dihydro-1,3-diazafluorene (2b) and 5,6,7,8,9,9-hexafluoro-4-trifluoromethyl-1,2-dihydro-1,3-diazafluorene-2-spiro-1′-cyclopentane (3b), respectively. When acted upon by (CH3)2SO4 compounds 2, 3 were converted into corresponding fluorine-containing 1-methyl-1,2-dihydro-1,3-diazafluorenes 6, 7. 4a-Chloro-5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-2,4a-dihydro-1,3-diazafluorene (8) has been synthesized by the interaction of compound 2 with SOCl2. Solution of compound 2 as well as 8 in CF3SO3H-CD2Cl2 generated 5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-1,2,3,4-tetrahydro-1,3-diazafluorene-4-yl cation (2c). The structures of compounds 2, 3, 6-8 have been determined by single crystal X-ray diffraction. 相似文献
3.
A bisphosphine in which a PhP-PPh bond bridges 1,8-positions of naphthalene, 1,2-dihydro-1,2-diphenyl-naphtho[1,8-cd]-1,2-diphosphole (1), was used as a bridging ligand for the preparation of dinuclear group 6 metal complexes. Free trans-1, a more stable isomer having two phenyl groups on phosphorus centers mutually trans with respect to a naphthalene plane, was allowed to react with two equivalents of M(CO)5(thf) (M = W, Mo, Cr) at room temperature to give dinuclear complexes (OC)5M(μ-trans-1)M(CO)5 (M = W (2a), Mo (2b), Cr (2c)). The preparation of the corresponding dinuclear complexes bridged by the cis isomer of 1 was also carried out starting from the free trans-1 in the following way. Mono-nuclear complexes M(trans-1)(CO)5 (M = W (3a), Mo (3b), Cr (3c)) which had been prepared by a reaction of trans-1 with one equivalent of the corresponding M(CO)5(thf) (M = W, Mo, Cr) complex, were heated in toluene, wherein a part of the trans-3a-c was converted to their respective cis isomer M(cis-1)(CO)5. Each cis trans mixture of the mono-nuclear complexes 3a-c was treated with the corresponding M(CO)5(thf) to give a cis trans mixture of the respective dinuclear complexes 2a-c. The cis isomer of the ditungsten complex 2a was isolated, and its molecular structure was confirmed by X-ray analysis, showing a shorter W?W distance of 5.1661(3) Å than that of 5.8317(2) Å in trans-2a. 相似文献
4.
The reactions of trans-[MoO(ONOMe)Cl2] 1 (ONOMe = methylamino-N,N-bis(2-methylene-4,6-dimethylphenolate) dianion) and trans-[MoO(ONOtBu)Cl2] 2 (ONOtBu = methylamino-N,N-bis(2-methylene-4-methyl-6-tert-butylphenolate) dianion) with PhNCO afforded new imido molybdenum complexes trans-[Mo(NPh)(ONOMe)Cl2] 3 and trans-[Mo(NPh)(ONOtBu)Cl2] 4, respectively. As analogous oxotungsten starting materials did not show similar reactivity, corresponding imido tungsten complexes were prepared by the reaction between [W(NPh)Cl4] with aminobis(phenol)s. These reactions yielded cis- and trans-isomers of dichloro complexes [W(NPh)(ONOMe)Cl2] 5 and [W(NPh)(ONOtBu)Cl2] 6, respectively. The molecular structures of 4, cis-6 and trans-6 were verified by X-ray crystallography. Organosubstituted imido tungsten(VI) complex cis-[W(NPh)(ONOtBu)Me2] 7 was prepared by the transmetallation reaction of 6 (either cis or trans isomer) with methyl magnesium iodide. 相似文献
5.
Charles E. Ellul 《Journal of organometallic chemistry》2010,695(1):6-2376
The reduction of trans-[Pd(NHC)2Cl2] (NHC = IMes, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; IiPr2 = 1,3-bis-isopropylimidazol-2-ylidene) with potassium graphite under an atmosphere of CO affords the palladium NHC carbonyl clusters [Pd3(μ-CO)3(NHC)3] (NHC = IMes, 1; IiPr2, 3). Treatment of 1 with SO2 at room temperature yields the bridging SO2 complex [Pd3(μ-SO2)3(IMes)3] (4) in quantitative yield. Complexes 1, 3 and 4 have been structurally characterised by X-ray crystallography. 相似文献
6.
Hayati Türkmen 《Journal of organometallic chemistry》2006,691(18):3749-3759
The synthesis of 1,3-diarylimidazolidin-2-ylidene (NHC) precursor, 1,3-bis(2,4,6-trimethylphenyl)imidazolinium chloride, (3b) has been extended to the electronically and sterically modified NHC precursors 3a (X = H), 3c (X = Br) and 3e (X = Cl) in order to investigate the electronic effect of a p-substituent (X) on cross-coupling catalysts. Complexes of the type PdCl2(NHC)2 (5), PdCl2(NHC)(PPh3) (6) and [RhCl(NHC)(cod)] (7) were prepared from 3 or 4d (1,3-bis(2,4-dimethylphenyl)-2-trichloromethylimidazolidin). Initial decomposition temperatures of the complexes 5 and 6 were determined by TGA. In situ formed complexes from Pd(OAc)2 and 3 as well as the preformed complexes 5 and 6 have been tested as catalysts in coupling of phenylboronic acid with 4-haloacetophenones. The electron donating ability of NHCs derived from 3 was assessed by measuring C-O frequencies in the respective [RhCl(NHC)(CO)2] complex 8 which was prepared by replacement of cod ligand of 7 with CO. An interesting correlation between the electron-donating nature of the aryl substituent and catalytic activity and also initial decomposition temperature of the complexes 5 and 6 was observed. 相似文献
7.
Title compounds of the type 2,3,5,6-tetraphenyl-1,4-di-X-1,4-di-Y-1,4-disilacyclohexa-2,5-diene wherein X=Y=NMe2 (4); X=NMe2, Y=Cl (cis, trans-5); X=NMe2, Y=Me [(trans)-6] and X=t-Bu, Y=Cl (trans-8) were synthesized from Si2(NMe2)5Cl, sym-Si2(NMe2)4Cl2, sym-Si2(NMe2)4Me2, and sym-Si2Cl4(t-Bu)2, respectively, in the presence of diphenylacetylene at 200 °C. Similarly the analogous title compound from the combination of 1-phenyl-1-propyne and Si2(NMe2)5Cl [X=Y=NMe2 (cis and trans-7) was synthesized. In all cases where cis/trans diastereomers could arise from two different silicon substituents (5, 6, 8) the trans isomer was the sole or dominant product. Evidence for the intermediacy of the silylene Si(NMe2)2 in these reactions was gained from a trapping experiment. Compound 4 upon treatment with SiCl4, SiBr4 or PI3 provided the corresponding 1,1,4,4-tetrahalo derivatives 9a-c, respectively. Treatment of 4 with MeOH or PhOH gave the 1,1,4,4-tetramethoxy and tetraphenoxy analogues 9d and 9e, respectively. The tetrachloro derivative 9a upon LAH reduction led to the corresponding tetrahydro compound 10, while the reaction of 9a with H2O gave the tetrahydroxy derivative 11. Allowing (trans)-6 to react with SiCl4 provided a ca. 1:1 cis/trans ratio of the derivative 12 in which X=Cl, Y=Me, and possible pathways that rationalize this loss of stereochemistry are proposed. Synthesis of trans-13 in which X=t-Bu, Y=H was achieved by LAH reduction of 8. All of the title compounds except 8 experience free phenyl rotation at room temperature. At −30 °C this rotation in 8 is essentially halted. The molecular structures of 4, 8, 9c, 9e, 10 and 13 were determined by X-ray crystallography. 相似文献
8.
N,N,N′,N′-Tetramethylmethanediamine (1a), N,N,N′,N′-tetramethylethanediamine (1b), N,N,N′,N′-tetramethyl-1,3-propanediamine (1c), and N,N,N′,N′-tetramethyl-1,6-hexanediamine (1d) were reacted at 25 °C with 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (2a), 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione (2b), 2-thenoyltrifluoroacetone (2c), and 4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione (2d) to form the ionic adducts 3-18. 1,4,7,10-Tetraazacyclododecane (1e) reacted at 25 °C with β-diketones (2a-d) and 1,1,1-trifluoro-2,4-pentanedione (2e) to give ionic solids 19-23 in good yields. Some of the products are liquid at 25 °C and are thermally stable over long liquid ranges as determined by thermal gravimetric analyses. Single-crystal X-ray structure determinations show that compounds 9 and 21 crystallize in the monoclinic space groups P2(1)/c and P2(1)/n, respectively. All the new compounds were characterized by 1H, 19F and 13C NMR, electrospray MS and/or elemental analyses. 相似文献
9.
Vladimir Nesterov Bhaskar Poola Michael G. Richmond 《Journal of organometallic chemistry》2007,692(9):1806-1811
The reaction between the triosmium cluster 1,2-Os3(CO)10(MeCN)2 and the diphosphine pincer ligand 4,6-bis(diphenylphosphinomethyl)-m-xylene (dppx) has been examined and found to yield the pincer-bridged cluster 1,2-Os3(CO)10(dppx) (2) as the major product, in addition to the pincer-bridged cluster 1,2-Os3(CO)10[1-diphenylphosphino-1-{(2,4-dimethyl-5-diphenylphosphinomethyl)phenyl}-propan-2-ol] (3) in trace amounts (<2% yield). Both cluster products have been isolated and their molecular structures determined by crystallographic analyses. The structural highlights of compounds 2 and 3, which represent the first examples of pincer-ligated metal clusters, are discussed. The origin of the functionalized diphosphine ligand in 3 is traced to the ethanol solvent that was used in the recrystallization of the dppx ligand. 相似文献
10.
Jorge Bravo Jesús Castro Ma Carmen Rodríguez-Martínez Stefano Antoniutti 《Journal of organometallic chemistry》2007,692(24):5481-5491
Hydride complex RuH2(PFFP)2 (1) [PFFP = (CF3CH2O)2PN(CH3)N(CH3)P(OCH2CF3)2] was prepared by allowing the compound RuCl4(bpy) · H2O (bpy = 1,2-bipyridine) to react first with the phosphite PFFP and then with NaBH4. Chloro-complex RuCl2(PFFP)2 (2) was also prepared, either by reacting RuCl4(bpy) · H2O with PFFP and zinc dust or by substituting triphenylphosphine with PFFP in the precursor complex RuCl2(PPh3)3. Hydride derivative RuH2(POOP)2 (3) (POOP = Ph2POCH2CH2OPPh2) was prepared by reacting compound RuCl3(AsPh3)2(CH3OH) first with the phosphite POOP and then with NaBH4. Depending on experimental conditions, treatment of carbonylated solutions of RuCl3 · 3H2O with POOP yields either the cis- or trans-RuCl2(CO)(PHPh2)(POOP) (4) derivative. Reaction of both cis- and trans-4 with LiAlH4 in thf affords dihydride complex RuH2(CO)(PHPh2)(POOP) (5). Chloro-complex all-trans-RuCl2(CO)2(PPh2OMe)2 (6) was obtained by reacting carbonylated solutions of RuCl3 · 3H2O in methanol with POOP. Treatment of chloro-complex 6 with NaBH4 in ethanol yielded hydride derivative all-trans-RuH2(CO)2(PPh2OMe)2 (7). The complexes were characterised spectroscopically and the X-ray crystal structures of complexes 1, 3, cis-4 and 6 were determined. 相似文献
11.
The reactions of Mo2(O2CCH3)4 with different equivalents of N,N′-bis(pyrimidine-2-yl)formamidine (HL1) and N-(2-pyrimidinyl)formamide (HL2) afforded dimolybdenum complexes of the types Mo2(O2CCH3)(L1)2(L2) (1) trans-Mo2(L1)2(L2)2 (2) cis-Mo2(L1)2(L2)2 (3) and Mo2(L2)4 (4). Their UV–Vis and NMR spectra have been recorded and their structures determined by X-ray crystallography. Complexes 2 and 3 establish the first pair of trans and cis forms of dimolybdenum complexes containing formamidinate ligands. The L1 ligands in 1–3 are bridged to the metal centers through two central amine nitrogen atoms, while the L2 ligands in 1–4 are bridged to the metal centers via one pyrimidyl nitrogen atom and the amine nitrogen atom. The Mo–Mo distances of complexes 1 [2.0951(17) Å], 2 [2.103(1) Å] and 3 [2.1017(3) Å], which contain both Mo?N and Mo?O axial interactions, are slightly longer than those of complex 4 [2.0826(12)–2.0866(10) Å] which has only Mo?O interactions. 相似文献
12.
Xavier Just-Baringo Paolo Bruno Fernando Albericio Mercedes Álvarez 《Tetrahedron letters》2011,52(42):5435-5437
(S)-2-(4-Bromo-2,4′-bithiazole)-1-(tert-butoxycarbonyl)pyrrolidine ((S)-1) was obtained as a single enantiomer and in high yield by means of a two-step modified Hantzsch thiazole synthesis reaction when bromoketone 3 and thioamide (S)-4 were used. Further conversion of (S)-1 into trimethyltin derivative (S)-2 broadens the scope for further cross-coupling reactions. 相似文献
13.
Gustavo Von Poelhsitz André L. Bogado Luciano M. Lião Antonio G. Ferreira Eduardo E. Castellano Javier Ellena Alzir A. Batista 《Polyhedron》2010
This study presents the syntheses and characterization of 2-mercaptopyridine (pyS−) complexes containing ruthenium(II) with the following general formula [Ru(pyS)2(P–P)], P–P = (c-dppen) = cis-1,2-bis(diphenylphosphino)ethylene) (1); (dppe) = 1,2-bis(diphenylphosphino)ethane (2); (dppp) = 1,3-bis(diphenylphosphino)propane (3) and (dppb) = 1,4-bis(diphenylphosphino)butane (4). The complexes were synthesized from the mer- or fac-[RuCl3(NO)(P–P)] precursors in the presence of triethylamine in methanol solution with dependence of the product on the P–P ligand. The reaction of pyS− with a ruthenium complex containing a bulky aromatic diphosphine dppb disclosed a major product with a dangling coordinated dppbO-P, the [Ru(pyS)2(NO)(η1-dppbO-P)]PF6(5). In addition, this work also presents and discusses the spectroscopic and electrochemical behavior of 1–5, and report the X-ray structures for 1 and 5. 相似文献
14.
Túlio F. Gallatti Gustavo Von Poelhsitz Eduardo E. Castellano Márcio P. de Araujo 《Journal of organometallic chemistry》2007,692(24):5447-5452
The synthesis and characterization of trans/cis-[RuCl2(dppf)(diimines)], dppf = 1,1′-bis(diphenylphosphino)ferrocene; diimines = 2,2′-bipyridine (trans/cis-(1)), the new complexes with 4,4′-dimethyl-2,2′-bipyridine (trans/cis-(2)) and 1,10-phenanthroline (cis-(3)) are presented. The complexes were synthesized using two routes and the trans/cis-isomer formation is dependent upon conditions and the precursor applied. The trans-isomer (kinetic) readily isomerizes to the cis-isomer (thermodynamic) when exposed to light (fluorescent) and this process was followed by cyclic voltammetry and UV-vis. The electrochemical studies on these complexes reveal that Fe(III)/Fe(II) couples are insensitive to the isomer (trans/cis) formed, but the Ru(III)/Ru(II) couples are dependent on the isomer. Transfer-hydrogenation reactions for reduction of acetophenone were conducted using complexes cis-(1) and cis-(2) and the results are compared with that obtained for similar complexes. X-ray structure for cis-(3) are presented and discussed. 相似文献
15.
Piotr Jaunky 《Journal of organometallic chemistry》2005,690(6):1429-1455
An efficient route to the novel tridentate phosphine ligands RP[CH2CH2CH2P(OR′)2]2 (I: R = Ph; R′ = i-Pr; II: R = Cy; R′ = i-Pr; III: R = Ph; R′ = Me and IV: R = Cy; R′ = Me) has been developed. The corresponding ruthenium and iron dicarbonyl complexes M(triphos)(CO)2 (1: M = Ru; triphos = I; 2: M = Ru; triphos = II; 3: M = Ru; triphos = III; 4: M = Ru; triphos = IV; 5: M = Fe; triphos = I; 6: M = Fe; triphos = II; 7: M = Fe; triphos = III and 8: M = Fe; triphos = IV) have been prepared and fully characterized. The structures of 1, 3 and 5 have been established by X-ray diffraction studies. The oxidative addition of MeI to 1-8 produces a mixture of the corresponding isomeric octahedral cationic complexes mer,trans-(13a-20a) and mer,cis-[M(Me)(triphos)(CO)2]I (13b-20b) (M = Ru, Fe; triphos = I-IV). The structures of 13a and 20a (as the tetraphenylborate salt (21)) have been verified by X-ray diffraction studies. The oxidative addition of other alkyl iodides (EtI, i-PrI and n-PrI) to 1-8 did not afford the corresponding alkyl metal complexes and rather the cationic octahedral iodo complexes mer,cis-[M(I)(triphos)(CO)2]I (22-29) (M = Ru, Fe; triphos = I-IV) were produced. Complexes 22-29 could also be obtained by the addition of a stoichiometric amount of I2 to 1-8. The structure of 22 has been verified by an X-ray diffraction study. Reaction of 13a/b-20a/b with CO afforded the acetyl complexes mer,trans-[M(COMe)(triphos)(CO)2]I, 30-37, respectively (M = Ru, Fe; triphos = I-IV). The ruthenium acetyl complexes 30-33 reacted slowly with 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) even in boiling acetonitrile. Under the same conditions, the deprotonation reactions of the iron acetyl complexes 34-37 were completed within 24-40 h to afford the corresponding zero valent complexes 5-8. It was not possible to observe the intermediate ketene complexes. Tracing of the released ketene was attempted by deprotonation studies on the labelled species mer,trans-[Fe(COCD3)(triphos)(CO)2]I (38) and mer,trans-[Fe(13COMe)(triphos)(CO)2]I (39). 相似文献
16.
Vijendra Kumar Fulwa 《Tetrahedron letters》2009,50(46):6264-182
Heating a neat 1:2 mixture of 2-picolylamine and 2-cyanopyridine followed by treatment of the resultant red gummy substance with aqueous KOH resulted in the isolation of 2,4,5-tris(2-pyridyl)imidazole (1a) as the major product and N-(3-(2-pyridyl)imidazo[1,5-a]pyridine)picolinamidine (2a) in small amounts. Similarly, by using 3-picolylamine, 2,4,-bis(2-pyridyl)-5-(3-pyridyl)imidazole (1b) and N-(3-(3-pyridyl)imidazo[1,5-a]pyridine)picolinamidine (2b) were isolated, and by using 4-picolylamine, 2,4,-bis(2-pyridyl)-5-(4-pyridyl)imidazole (1c) and N-(3-(4-pyridyl)imidazo[1,5-a]pyridine)picolinamidine (2c) were isolated. The plausible mechanism of the formation of 1a-c and 2a-c is delineated. 相似文献
17.
Ekkehardt F. Hahn Beate Heidrich Alexander Hepp Tania Pape 《Journal of organometallic chemistry》2007,692(21):4630-4638
N-Heterocyclic carbene ligands (NHC) were metalated with Pd(OAc)2 or [Ni(CH3CN)6](BF4)2 by in situ deprotonation of imidazolium salts to give the N-olefin functionalized biscarbene complexes [MX2(NHC)2] 3-7 (3: M = Pd, X = Br, NHC = 1,3-di(3-butenyl)imidazolin-2-ylidene; 4: M = Pd, X = Br, NHC = 1,3-di(4-pentenyl)imidazolin-2-ylidene; 5: M = Pd, X = I, NHC = 1,3-diallylimidazolin-2-ylidene; 6: M = Ni, X = I, NHC = 1,3-diallylimidazolin-2-ylidene; 7: M = Ni, X = I, NHC = 1-methyl-3-allylimidazolin-2-ylidene). Molecular structure determinations for 4-7 revealed that square-planar complexes with cis (5) or trans (4, 6, 7) coordination geometry at the metal center had been obtained. Reaction of nickelocene with imidazolium bromides afforded the η5-cyclopentadienyl (η5-Cp) monocarbene nickel complexes [NiBr(η5-Cp)(NHC)] 8 and 9 (8: NHC = 1-methyl-3-allylimidazolin-2-ylidene; 9: NHC = 1,3-diallylimidazolin-2-ylidene). The bromine abstraction in complexes 8 and 9 with silver tetrafluoroborate gave complexes [NiBr(η5-Cp)(η3-NHC)] 10 and 11. The X-ray structure analysis of 10 and 11 showed a trigonal-pyramidal coordination geometry at the nickel(II) center and coordination of one N-allyl substituent. 相似文献
18.
Reactions of 0.5 eq. of the dinuclear complexes [(η6-arene)Ru(μ-Cl)Cl]2 (arene = η6-C6H6, η6-p-iPrC6H4Me) and [(Cp∗)M(μ-Cl)Cl]2 (M = Rh, Ir; Cp∗ = η5-C5Me5) with 4,6-disubstituted pyrazolyl-pyrimidine ligands (L) viz. 4,6-bis(pyrazolyl)pyrimidine (L1), 4,6-bis(3-methyl-pyrazolyl)pyrimidine (L2), 4,6-bis(3,5-dimethyl-pyrazolyl)pyrimidine (L3) lead to the formation of the cationic mononuclear complexes [(η6-C6H6)Ru(L)Cl]+ (L = L1, 1; L2, 2; L3, 3), [(η6-p-iPrC6H4Me)Ru(L)Cl]+ (L = L1, 4; L2, 5; L3, 6), [(Cp∗)Rh(L)Cl]+ (L = L1, 7; L2, 8; L3, 9) and [(Cp∗)Ir(L)Cl]+ (L = L1, 10; L2, 11; L3, 12), while reactions with 1.0 eq. of the dinuclear complexes [(η6-arene)Ru(μ-Cl)Cl]2 and [(Cp∗)M(μ-Cl)Cl]2 give rise to the dicationic dinuclear complexes [{(η6-C6H6)RuCl}2(L)]2+ (L = L1, 13; L2, 14; L3, 15), [{(η6-p-iPrC6H4Me)RuCl}2(L)]2+ (L = L1, 16; L2, 17; L3, 18), [{(Cp∗)RhCl}2(L)]2+ (L = L1, 19; L2, 20; L3, 21) and [{(Cp∗)IrCl}2(L)]2+ (L = L1 22; L2, 23; L3 24). The molecular structures of [3]PF6, [6]PF6, [7]PF6 and [18](PF6)2 have been established by single crystal X-ray structure analysis. 相似文献
19.
New palladium(II) and platinum(II) complexes of saccharinate (sac), trans-[Pd(py)2(sac)2] (1), cis-[Pt(py)2(sac)2] (2), trans-[Pd(3-acpy)2(sac)2] (3) and cis-[Pt(3-acpy)2(sac)2] (4) (py = pyridine and 3-acpy = 3-acetylpyridine) have been synthesized. Elemental analysis, UV-Vis, IR, NMR and TG/DTA characterizations have been carried out. The structures of 1-4 were determined by X-ray diffraction. The palladium(II) and platinum(II) ions are coordinated by two N-bonded sac ligands, and two nitrogen atoms of py or 3-acpy, forming a distorted square-planar geometry. The palladium(II) complexes (1 and 3) are trans isomers, while the platinum(II) complexes (2 and 4) are cis isomers. The mononuclear species in the solid state are connected by weak intermolecular C-H?O hydrogen bonds, C-H?π and π?π stacking interactions. The platinum(II) complexes show significant fluorescence at the room temperature. 相似文献
20.
Anna Louisa Noffke Wim Wätjen Bernhard Spingler Peter C. Kunz 《Journal of organometallic chemistry》2011,696(5):1096-10800
The tetranuclear ruthenium arene compound [(cym)4Ru4(2)Cl6]Cl2 (3) (cym = η6-p-cymene, 2 = 1,2-bis(di-N-methylimidazol-2-ylphosphino)ethane) was prepared and characterised by one- and two-dimensional NMR techniques. Its cytotoxicity against four different cell lines was determined and, with an approximate IC50 of >100 μM 3 can be regarded as non-toxic. Its partition coefficient in n-octanol/water (log D7.4) was also determined. The structures of complex 3 as well as of the related compound [(cym)2Ru2(4)Cl2]Cl2 (5) (4 = 1,2-bis(di-N-methylimidazol-2-ylphosphino)ethane dioxide) were determined by single crystal structure analysis. Upon oxidation in protic solvents, ligand 2 shows P-C bond cleavage reactions to yield P,P′-bis(N-methylimidazol-2-yl)ethylene diphosphinic acid (6). 相似文献