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1.
Massimo Di Vaira Fabrizio Mani Piero Stoppioni 《Journal of organometallic chemistry》2004,689(10):1757-1762
The reaction of [CpRu(CH3CN)3]PF6 with the bidentate ligands L-L=1,2-bis(diphenylphosphino)ethane, dppe, and (1-diphenylarsino-2-diphenylphosphino)ethane, dpadppe, affords mononuclear or dinuclear complexes of formula [CpRu(η2-L-L)(CH3CN)]PF6, [{CpRu(CH3CN)2}2(μ-η1:1-L-L)](PF6)2 and [{CpRu(CH3CN)}2(μ-η1:1-L-L)2](PF6)2 (L-L=dppe, dpadppe). All of the compounds are characterized by microanalysis and NMR [1H and 31P{1H}] spectroscopy. The crystal structure of [{CpRu(CH3CN)2}2(μ-η1:1-dppe)](PF6)2 has been determined by X-ray diffraction analysis. The complex exhibits a dppe ligand bridging two CpRu(CH3CN)2 fragments. 相似文献
2.
Ledger AE Ellul CE Mahon MF Williams JM Whittlesey MK 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(31):8704-8713
Addition of the amine–boranes H3B ? NH2tBu, H3B ? NHMe2 and H3B ? NH3 to the cationic ruthenium fragment [Ru(xantphos)(PPh3)(OH2)H][BArF4] ( 2 ; xantphos=4,5‐bis(diphenylphosphino)‐9,9‐dimethylxanthene; BArF4=[B{3,5‐(CF3)2C6H3}4]?) affords the η1‐B? H bound amine–borane complexes [Ru(xantphos)(PPh3)(H3B ? NH2tBu)H][BArF4] ( 5 ), [Ru(xantphos)(PPh3)(H3B ? NHMe2)H][BArF4] ( 6 ) and [Ru(xantphos)(PPh3)(H3B ? NH3)H][BArF4] ( 7 ). The X‐ray crystal structures of 5 and 7 have been determined with [BArF4] and [BPh4] anions, respectively. Treatment of 2 with H3B ? PHPh2 resulted in quite different behaviour, with cleavage of the B? P interaction taking place to generate the structurally characterised bis‐secondary phosphine complex [Ru(xantphos)(PHPh2)2H][BPh4] ( 9 ). The xantphos complexes 2 , 5 and 9 proved to be poor precursors for the catalytic dehydrogenation of H3B ? NHMe2. While the dppf species (dppf=1,1′‐bis(diphenylphosphino)ferrocene) [Ru(dppf)(PPh3)HCl] ( 3 ) and [Ru(dppf)(η6‐C6H5PPh2)H][BArF4] ( 4 ) showed better, but still moderate activity, the agostic‐stabilised N‐heterocyclic carbene derivative [Ru(dppf)(ICy)HCl] ( 12 ; ICy=1,3‐dicyclohexylimidazol‐2‐ylidene) proved to be the most efficient catalyst with a turnover number of 76 h?1 at room temperature. 相似文献
3.
Suzanne Burling Dr. L. Jonas L. Häller Dr. Elena Mas‐Marzá Dr. Aitor Moreno Stuart A. Macgregor Prof. Mary F. Mahon Dr. Paul S. Pregosin Prof. Dr. Michael K. Whittlesey Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(41):10912-10923
The five‐coordinate ruthenium N‐heterocyclic carbene (NHC) hydrido complexes [Ru(IiPr2Me2)4H][BArF4] ( 1 ; IiPr2Me2=1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene; ArF=3,5‐(CF3)2C6H3), [Ru(IEt2Me2)4H][BArF4] ( 2 ; IEt2Me2=1,3‐diethyl‐4,5‐dimethylimidazol‐2‐ylidene) and [Ru(IMe4)4H][BArF4] ( 3 ; IMe4=1,3,4,5‐tetramethylimidazol‐2‐ylidene) have been synthesised following reaction of [Ru(PPh3)3HCl] with 4–8 equivalents of the free carbenes at ambient temperature. Complexes 1 – 3 have been structurally characterised and show square pyramidal geometries with apical hydride ligands. In both dichloromethane or pyridine solution, 1 and 2 display very low frequency hydride signals at about δ ?41. The tetramethyl carbene complex 3 exhibits a similar chemical shift in toluene, but shows a higher frequency signal in acetonitrile arising from the solvent adduct [Ru(IMe4)4(MeCN)H][BArF4], 4 . The reactivity of 1 – 3 towards H2 and N2 depends on the size of the N‐substituent of the NHC ligand. Thus, 1 is unreactive towards both gases, 2 reacts with both H2 and N2 only at low temperature and incompletely, while 3 affords [Ru(IMe4)4(η2‐H2)H][BArF4] ( 7 ) and [Ru(IMe4)4(N2)H][BArF4] ( 8 ) in quantitative yield at room temperature. CO shows no selectivity, reacting with 1 – 3 to give [Ru(NHC)4(CO)H][BArF4] ( 9 – 11 ). Addition of O2 to solutions of 2 and 3 leads to rapid oxidation, from which the RuIII species [Ru(NHC)4(OH)2][BArF4] and the RuIV oxo chlorido complex [Ru(IEt2Me2)4(O)Cl][BArF4] were isolated. DFT calculations reproduce the greater ability of 3 to bind small molecules and show relative binding strengths that follow the trend CO ? O2 > N2 > H2. 相似文献
4.
Dr. Adinarayana Doddi Dr. Dirk Bockfeld Dr. Thomas Bannenberg Prof. Dr. Matthias Tamm 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(65):14878-14887
Chloride abstraction from the complexes [(η6-p-cymene){(IDipp)P}MCl] ( 2 a , M=Ru; 2 b , M=Os) and [(η5-C5Me5){(IDipp)P}IrCl] ( 3 b , IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBArF) in the presence of trimethylphosphine (PMe3), 1,3,4,5-tetramethylimidazolin-2-ylidene (MeIMe) or carbon monoxide (CO) afforded the complexes [(η6-p-cymene){(IDipp)P}M(PMe3)]BArF] ( 4 a , M=Ru; 4 b , M=Os), [(η6-p-cymene){(IDipp)P}Os(MeIMe)]BArF] ( 5 ) and [(η5-C5Me5){(IDipp)P}IrL][BArF] ( 6 , L=PMe3; 7 , L=MeIMe; 8 , L=CO). These cationic N-heterocyclic carbene-phosphinidene complexes feature very similar structural and spectroscopic properties as prototypic nucleophilic arylphosphinidene complexes such as low-field 31P NMR resonances and short metal-phosphorus double bonds. Density functional theory (DFT) calculations reveal that the metal-phosphorus bond can be described in terms of an interaction between a triplet [(IDipp)P]+ cation and a triplet metal complex fragment ligand with highly covalent σ- and π-contributions. Crystals of the C−H activated complex 9 were isolated from solutions containing the PMe3 complex, and its formation can be rationalized by PMe3 dissociation and formation of a putative 16-electron intermediate [(η5-C5Me5)Ir{P(IDipp)}I][BArF], which undergoes C−H activation at one of the Dipp isopropyl groups and addition along the iridium-phosphorus bond to afford an unusual η3-benzyl coordination mode. 相似文献
5.
S. V. Safronov A. M. Sheloumov P. V. Petrovskii M. G. Ezernitskaya A. A. Koridze 《Russian Chemical Bulletin》2012,61(11):2065-2069
The reaction of [CpRu(CH3CN)3][PF6], [Cp*RuCl] n , and [CpFRuCl]n with 1,3-diformylindene results in the predominant formation of zwitter-ionic arene-cyclopentadienyl complexes {η6-1,3-(CHO)2C9H5}RuCp (Cp = C5H5), {η6-1,3-(CHO)2C9H5}RuCp* (Cp* = C5Me5), and {η6-1,3-(CHO)2C9H5}RuCpF (CpF = C5Me4CF3), respectively. The ruthenocenes {η5-1,3-(CHO)2C9H5}RuCp, {η5-1,3-(CHO)2C9H5}RuCp*, and {η5-1,3-(CHO)2C9H5}RuCpF were synthesized by the reaction of 1,3-diformylindenyl potassium with [CpRu(CH3CN)3][PF6], [Cp*RuCl] n , and [CpFRuCl] n . 相似文献
6.
Syntheses and Structures of Ruthenium Complexes Containing a Ru‐H‐Tl Three‐Center–Two‐Electron Bond
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Dr. Wei Bai Jing‐Xuan Zhang Dr. Ting Fan Dr. Sunny Kai San Tse Dr. Wangge Shou Dr. Herman H. Y. Sung Prof. Dr. Ian D. Williams Prof. Dr. Zhenyang Lin Prof. Dr. Guochen Jia 《Angewandte Chemie (International ed. in English)》2018,57(39):12874-12879
Treatment of CpRuH(PP) (PP=dppm, dppe) with TlPF6 produced [CpRu(H)(Tl)(PP)]PF6. X‐ray diffraction and computational studies suggest that the complexes contain a Ru?H?Tl 3c–2e bond and can be viewed as the first σ‐complexes of period 6 main‐group hydrides [CpRu{η2‐(H?Tl)}(PP)]PF6 or [Tl{η2‐H?RuCp(PP)}]PF6. The complexes can be stored as a solid at room temperature for days without appreciable decomposition, but are unstable in solution and evolved to the trimetallic complexes [{CpRu(PP)}2(μ‐Tl)]PF6. 相似文献
7.
Eva Bocekova‐Gajdoíkova Bugra Epik Jingyu Chou Katsuhiro Akiyama Nobuaki Fukui Laure Gune E. Peter Kündig 《Helvetica chimica acta》2019,102(5)
Details of the direct synthesis of cationic Ru(II)(η5‐Cp)(η6‐arene) complexes from ruthenocene using microwave heating are reported. Developed for the important catalyst precursor [Ru(II)(η5‐Cp)(η6‐1‐4,4a,8a‐naphthalene)][PF6] reaction time could be shortened from three days to 15 min. The method was extended to [Ru(II)(η6‐benzene)(η5‐Cp)][PF6], [Ru(II)(η5‐Cp)(η6‐toluene)][PF6], [Ru(II)(η5‐Cp)(η6‐mesitylene)][PF6], [Ru(II)(η5‐Cp)(η6‐hexamethylbenzene)][PF6], [Ru(II)(η5Cp)(η6‐indane)][PF6], [Ru(II)(η5‐Cp)(η6‐2,6‐dimethylnaphthalene)][PF6], and [Ru(II)(η5‐Cp)(η6‐pyrene)][PF6]. 1‐methylnaphthalene and 2,3‐dimethylnaphthalene afforded mixtures of regioisomeric complexes. [Ru(Cp)(CH3CN)3][PF6], derived from the naphthalene precursor provided access to the cationic RuCp complexes of naphthoquinone, tetralindione, 1,4‐dihydroxynaphthalene, and 1,4‐dimethoxynaphthalene. Reduction of the tetralindione complex afforded selectively the endo,endo diol derivative. X‐Ray structures of five complexes are reported. 相似文献
8.
[CpRu(dppf)Cl] (Cp=η5-C5H5) (1) and [(HMB)Ru(dppf)Cl]PF6 ((HMB)=η6-C6Me6) (3) react with different donor ligands to give rise to N-, P- and S-bonded complexes. The stoichiometric reactions of 1 and 3 with NaNCS give the mononuclear complexes [CpRu(dppf)(NCS)] (2) and [(HMB)Ru(dppf)(NCS)]PF6 (4), respectively, in yields above 80%, while 3 also gives a dppf-bridged diruthenium complex [(HMB)Ru(NCS)2]2(μ-dppf) (5) in 67% yield from reaction with four molar equivalents of NaNCS. Compound 5 is also obtained in 70% yield from the reaction of 4 with excess NaNCS. With CH3CN in the presence of salts, both 1 and 3 give their analogous solvento derivatives [CpRu(dppf)(CH3CN)]BPh4 (6) and [(HMB)Ru(dppf)(CH3CN)] (PF6)2 (7). With phosphines, the reaction of 1 gives chloro-displaced complexes [(CpRu(dppf)L]PF6 (L =PMe3 (8), PMe2Ph(9)), whereas the reaction of 3 with PMe2Ph leads to substitution of dppf, giving [(HMB)Ru(PMe2Ph)2Cl] PF6 (10). The reaction of 1 with NaS2CNEt2 gives a dinuclear dppf-bridged complex [{CpRu(S2CNEt2)}2(μ-dppf)] (11), whereas that of 3 results in loss of the HMB ligand giving a mononuclear complex [Ru(dppf)(S2CNEt2)2] (12). With elemental sulfur S8, 1 is oxidized to give a dinuclear CpRuIII dppf-chelated complex [{CpRu(dppf)}2(μ-S2)](BPh4)Cl (13), whereas 3 undergoes oxidation at the ligand, giving a dppf-displaced complex [(HMB)Ru(CH3CN)2Cl]PF6 (14) and free dppfS2. The structures of 1, 2, 5-9, 11, 13 and 14 were established by X-ray single crystal diffraction analyses. Of these, 5 and 11 both contain a dppf-bridge between RuII centers, while 13 is a dinuclear CpRuIII disulfide-bridged complex; all the others are mononuclear. All complexes obtained were also spectroscopically characterized. 相似文献
9.
Richard E. Douthwaite Neil Guillaume Adrian C. Whitwood 《Journal of organometallic chemistry》2006,691(4):711-716
Reaction between 9,9′-spirobifluorene and [CpM]+ (where M = Fe and Ru) equivalents gives the complexes [CpRu(η6-SBF)][PF6] (1), [(CpRu)2(η6,η6-SBF)][PF6]2 (2) and [(CpFe)2(η6,η6-SBF)][PF6]2 (3), respectively. Single crystal X-ray structures of 1 and 3 show that the metal atoms exhibit distorted η6-coordination to SBF phenyl moieties primarily as a consequence of steric interactions between Cp and SBF. The structure of 3 contains each of the possible C2 enantiomers whereas NMR spectroscopy shows signals consistent with a 1:1 mixture of C2 and C1 stereoisomers for both 2 and 3. In conjunction with electrochemical data the observations are consistent with SBF acting as a molecule containing two independent biphenyl moieties. 相似文献
10.
Isolation and Structure of Germylene‐Germyliumylidenes Stabilized by N‐Heterocyclic Imines
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MSc. Tatsumi Ochiai Dr. Tibor Szilvási Dr. Daniel Franz Dr. Elisabeth Irran Prof. Dr. Shigeyoshi Inoue 《Angewandte Chemie (International ed. in English)》2016,55(38):11619-11624
The ditopic germanium complex FGe(NIPr)2Ge[BF4] ( 3 [BF4]; IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene) is prepared by the reaction of the amino(imino)germylene (Me3Si)2NGeNIPr ( 1 ) with BF3?OEt2. This monocation is converted into the germylene‐germyliumylidene 3 [BArF4] [ArF=3,5‐(CF3)2‐C6H3] by treatment with Na[BArF4]. The tetrafluoroborate salt 3 [BF4] reacts with 2 equivalents of Me3SiOTf to give the novel complex (OTf)(GeNIPr)2[OTf] ( 4 [OTf]), which affords 4 [BArF4] and 4 [Al(ORF)4] [RF=C(CF3)3] after anion exchange with Na[BArF4] or Ag[Al(ORF)4], respectively. The computational, as well as crystallographic study, reveals that 4 + has significant bis(germyliumylidene) dication character. 相似文献
11.
Ilia A. Guzei Brian S. Dolinar Nozipho Khumalo James Darkwa 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(8):847-850
In (η6‐p‐cymene)(difluorophosphinato‐κO){2‐[(1H‐pyrazol‐1‐yl)methyl‐κN2]pyridine‐κN}ruthenium(II) 0.85‐hexafluorophosphate 0.15‐tetrafluoroborate, [Ru(PO2F2)(C10H14)(C9H9N3)](PF6)0.85(BF4)0.15, (I), the [PO2F2]− ligand exhibits positional disorder due to one F atom and one O atom sharing the same two positions related by a mirror reflection across the O—P—F plane. The correct composition of this coordinated anion was successfully determined to be [PO2F2]− by refining the complex with various tetrahedral anions in which terminal atoms have similar atomic form factors. The noncoordinated counter‐ion is compositionally disordered between [PF6]− and [BF4]−. The difficulty in determining the correct composition of this anion illustrates the importance of a crystallographer remaining impartial and open to encountering unexpected moieties in the process of elucidating a structure. 相似文献
12.
Ayumi Suzuki Dr. Yuichiro Mutoh Dr. Noriko Tsuchida Chi-Wai Fung Dr. Shoko Kikkawa Prof. Isao Azumaya Prof. Shinichi Saito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(17):3795-3802
Although the chemistry of transition-metal complexes with carbonyl (CO) and thiocarbonyl (CS) ligands has been well developed, their heavier analogues, namely selenocarbonyl (CSe) and tellurocarbonyl (CTe) complexes remain scarce. The limited availability of such CSe and CTe complexes has so far hampered our understanding of the differences between such chalcogenocarbonyl (CE: E=O, S, Se, Te) ligands. Herein, we report the synthesis and properties of a series of cationic half-sandwich ruthenium CE complexes of the type [CpRu(CE)(H2IMes)(CNCH2Ts)][BArF4] (Cp=η5-C5H5−; H2IMes=1,3-dimesitylimidazolin-2-ylidene; ArF=3,5-(CF3)2C6H3). A combination of X-ray diffraction analyses, NMR spectroscopic analyses, and DFT calculations revealed an increasing π-accepting ability of the CE ligands in the order O<S<Se<Te. A variable-temperature NMR analysis of the thus obtained chiral-at-metal CE complexes indicated high stereochemical stability. 相似文献
13.
Dr. Sören Arlt Dr. Kevin Bläsing Dr. Jörg Harloff Karoline Charlotte Laatz Dr. Dirk Michalik Simon Nier Prof. Axel Schulz Philip Stoer Dr. Alrik Stoffers Dr. Alexander Villinger 《ChemistryOpen》2021,10(2):62-71
Within the second funding period of the SPP 1708 “Material Synthesis near Room Temperature”,which started in 2017, we were able to synthesize novel anionic species utilizing Ionic Liquids (ILs) both, as reaction media and reactant. ILs, bearing the decomposable and non-innocent methyl carbonate anion [CO3Me]−, served as starting material and enabled facile access to pseudohalide salts by reaction with Me3Si−X (X=CN, N3, OCN, SCN). Starting with the synthesized Room temperature Ionic Liquid (RT-IL) [nBu3MeN][B(OMe)3(CN)], we were able to crystallize the double salt [nBu3MeN]2[B(OMe)3(CN)](CN). Furthermore, we studied the reaction of [WCC]SCN and [WCC]CN (WCC=weakly coordinating cation) with their corresponding protic acids HX (X=SCN, CN), which resulted in formation of [H(NCS)2]− and the temperature labile solvate anions [CN(HCN)n]− (n=2, 3). In addition, the highly labile anionic HCN solvates were obtained from [PPN]X ([PPN]=μ-nitridobis(triphenylphosphonium), X=N3, OCN, SCN and OCP) and HCN. Crystals of [PPN][X(HCN)3] (X=N3, OCN) and [PPN][SCN(HCN)2] were obtained when the crystallization was carried out at low temperatures. Interestingly, reaction of [PPN]OCP with HCN was noticed, which led to the formation of [P(CN)2]−, crystallizing as HCN disolvate [PPN][P(CN⋅HCN)2]. Furthermore, we were able to isolate the novel cyanido(halido) silicate dianions of the type [SiCl0.78(CN)5.22]2− and [SiF(CN)5]2− and the hexa-substituted [Si(CN)6]2− by temperature controlled halide/cyanide exchange reactions. By facile neutralization reactions with the non-innocent cation of [Et3HN]2[Si(CN)6] with MOH (M=Li, K), Li2[Si(CN)6] ⋅ 2 H2O and K2[Si(CN)6] were obtained, which form three dimensional coordination polymers. From salt metathesis processes of M2[Si(CN)6] with different imidazolium bromides, we were able to isolate new imidazolium salts and the ionic liquid [BMIm]2[Si(CN)6]. When reacting [Mes(nBu)Im]2[Si(CN)6] with an excess of the strong Lewis acid B(C6F5)3, the voluminous adduct anion {Si[CN⋅B(C6F5)3]6}2− was obtained. 相似文献
14.
Haritosh Mishra 《Journal of organometallic chemistry》2010,695(14):1753-332
Structural analysis of a previously reported half-sandwich complex having three-legged “piano-stool” geometry [(η6-C6H6)RuII(L1)Cl][PF6] (1) (L1 = 2-(pyrazol-1-ylmethyl)pyridine) is described. Treatment of 1 with (i) Ag(CF3SO3) in CH3CN and (ii) NaN3 in CH3OH, and (iii) the reaction between [(η6-C6H6)Ru(L2)Cl]-[PF6] (2) (previously reported) and NaCN in C2H5OH led to the isolation of [(η6-C6H6)Ru(L1)(CH3CN)][PF6]2 (3), [(η6-C6H6)Ru(L1)(N3)][PF6] (4), and [(η6-C6H6)Ru(L2)(CN)][PF6] (5), respectively (L2 = 2-(3,5-dimethyl-pyrazol-1-ylmethyl)pyridine). The complex [(η6-C6H6)Ru(L4)Cl][PF6] (6) with a new ligand (L4 = 2-[3-(4-fluorophenyl)pyrazol-1-ylmethyl]pyridine) has also been synthesized. The structures of 3-6 have been elucidated (1H NMR spectra; CD3CN). The molecular structures of 1, 4, and 6·C6H5CH3 have been determined. Notably, the crystal-packing in these structures is governed by C-H?X (X = Cl, N) interactions, generating helical architectures. 相似文献
15.
Stephen Massicot Tomoya Sasaki Dr. Matthias Lexow Dr. Florian Maier Prof. Dr. Susumu Kuwabata Prof. Dr. Hans-Peter Steinrück 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(28):e202200167
We investigated the adsorption, surface enrichment, ion exchange, and on-surface metathesis of ultrathin mixed IL films on Ag(111). We stepwise deposited 0.5 ML of the protic IL diethylmethylammonium trifluoromethanesulfonate ([dema][TfO]) and 1.0 ML of the aprotic IL 1-methyl-3-octylimidazolium hexafluorophosphate ([C8C1Im][PF6]) at around 90 K. Thereafter, the resulting layered frozen film was heated to 550 K, and the thermally induced phenomena were monitored in situ by angle-resolved X-ray photoelectron spectroscopy. Between 135 and 200 K, [TfO]− anions at the Ag(111) surface are exchanged by [PF6]− anions and enriched together with [C8C1Im]+ cations at the IL/vacuum interface. Upon further heating, [dema][PF6] and [OMIm][PF6] desorb selectively at ∼235 and ∼380 K, respectively. Hereby, a wetting layer of pure [C8C1Im][TfO] is formed by on-surface metathesis at the IL/metal interface, which completely desorbs at ∼480 K. For comparison, ion enrichment at the vacuum/IL interface was also studied in macroscopic IL mixtures, where no influence of the solid support is expected. 相似文献
16.
The reactions of [Co(η-C5H5)(L)I2] with Na[S2CNR2] (R = alkyl or phenyl) give [Co(η-C5H5)(I)(S2CNR2)] (I) when L = CO and [Co(η-C5H5)(L)(S2CNR2)]I (II) when L is a tertiary phosphine, phosphite or stibine, or organo-isocyanide ligand. In similar reactions [Co(η-C5H5)(CO)(C3F7)I] gives [Co(η-C5H5)(C3F7)(S2CNMe2)] and [Mn(η-MeC5H4)(CO)2(NO)]PF6 forms [Mn(η-MeC5H4)(NO)(S2CNR2)]. The iodide ligands in I may be displaced by L, to give II, or by other ligands such as [CN]?, [NCS]?, H2O or pyridine whilst SnCl2 converts it to SnCl2I. The iodide counter-anion in II may be replaced by others to give [BPh4]?, [Co(CO)4]? or [NO3]? salts. However [CN]? acts differently and displaces (PhO)3P from [Co(η-C5H5){P(OPh)3}(S2CNMe)]I to give [Co(η-C5H5)(CN)(S2CNMe2)] which may be alkylated reversibly by MeI and irreversibly by MeSO3F to [Co(η-C5H5)(CNMe)(S2CNMe2)]+ salts. Conductivity measurements suggest that solutions of I in donor solvents are partially ionized with the formation of [Co(η-C5H5)(solvent)(S2CNR2)]+ I? species. The IR and 1H NMR spectra of the various complexes are reported. They are consistent with pseudo-octahedral “pianostool” molecular structures in which the bidentate dithiocarbamate ligands are coordinated to the metal atoms through both sulphur atoms. 相似文献
17.
Christoph Riesinger Luis Dütsch Dr. Gábor Balázs Dr. Michael Bodensteiner Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(71):17165-17170
The reaction of [Cp′′′Ni(η3-P3)] ( 1 ) with in situ generated phosphenium ions [RR′P]+ yields the unprecedented polyphosphorus cations of the type [Cp′′′Ni(η3-P4R2)][X] (R=Ph ( 2 a ), Mes ( 2 b ), Cy ( 2 c ), 2,2′-biphen ( 2 d ), Me ( 2 e ); [X]−=[OTf]−, [SbF6]−, [GaCl4]−, [BArF]−, [TEF]−) and [Cp′′′Ni(η3-P4RCl)][TEF] (R=Ph ( 2 f ), tBu ( 2 g )). In the reaction of 1 with [Br2P]+, an analogous compound is observed only as an intermediate and the final product is an unexpected dinuclear complex [{Cp′′′Ni}2(μ,η3:η1:η1-P4Br3)][TEF] ( 3 a ). A similar product [{Cp′′′Ni}2(μ,η3:η1:η1-P4(2,2′-biphen)Cl)][GaCl4] ( 3 b ) is obtained, when 2 d [GaCl4] is kept in solution for prolonged times. Although the central structural motif of 2 a – g consists of a “butterfly-like” folded P4 ring attached to a {Cp′′′Ni} fragment, the structures of 3 a and 3 b exhibit a unique asymmetrically substituted and distorted P4 chain stabilised by two {Cp′′′Ni} fragments. Additional DFT calculations shed light on the reaction pathway for the formation of 2 a – 2 g and the bonding situation in 3 a . 相似文献
18.
D.E. Games L.A.P. Kane-Maguire D.A. Sweigart 《Journal of organometallic chemistry》1982,234(3):323-327
Field desorption mass spectra are reported for a range of [M(CO)3(η-arene)]X (MMn or Re, XBF4 or PF6) salts. In most cases the spectra are simple, being dominated by molecular, [M]+·, [M + 1]+, and [MCO]+ ions for the cationic part of their structure. However, with the π-chloroarene complexes [Mn(CO)3(η-ClC6H5)]PF6 and [Mn(CO)3(η-1-Cl, 4-MeC6H4)]PF6, facile loss of the chloro substituent and further fragmentation leads to unusually complex spectra, which include strong peaks arising from recombination of fragment species. Cluster ions are also noted in several cases, allowing identification of the anion. 相似文献
19.
Stefan Nikolić Sanja Grgurić-Šipka Ivana S. Djordjević Rahma Dahmani Dragana Dekanski Sašenka Vidičević 《Journal of Coordination Chemistry》2019,72(1):148-163
In search for antitumor metal-based drugs that would mitigate the severe side-effects of cisplatin, Ru(II) complexes are gaining increasing recent interest. In this work, we report on the synthesis, characterization (1H- and 13C-NMR, FT-IR), and cytotoxicity studies of two new half-sandwich organometallic Ru(II) complexes of the general formula [Ru(η6-arene)(XY)Cl](PF6) where arene?=?benzene or toluene and XY?=?bidentates: dipyrido[3,2-a:2′,3′-c]phenazine (dppz) or 2-(9-anthryl)-1H-imidazo[4,5-f][1,10]phenanthroline (aip), which are bound to Ru(II) via two phenanthroline-N atoms in a characteristic “piano-stool” configuration of Ru(II)-arene complexes—as confirmed by vibrational and NMR spectra. In addition, cytotoxic studies were performed for similar half-sandwich organometallic [Ru(η6-p-cymene)(Me2dppz)Cl]PF6 complex (Me2dppz = 11,12-dimethyl-dipyrido[3,2-a:2′,3′-c]phenazine). This study is complemented with elaborate modeling with density functional theory (DFT) calculations, which provided insight into reactive sites of Ru(II) structures, further detailed by molecular docking on the B-DNA dodecamer, which identified binding sites and affinities: most pronounced for the [Ru(η6-benzene)(aip)Cl](PF6) in both A-T and G-C regions of the DNA minor groove. Cytotoxic activity was probed versus tumor cell lines B16, C6, and U251 (B16 mouse melanoma, C6 rat glioma, U251 human glioblastoma) and non-tumor cell line HACAT (HACAT normal human keratinocytes). 相似文献
20.
Dicopper complexes catalyzed coupling/cyclization of 2‐bromobenzoic acids with amidines leading to quinazolinones
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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