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1.
Ansa‐Complexes of [Mn(η5‐C5H5)(η6‐C6H6)]: Preparation,Characterization, and Reactivity of [n]Manganoarenophanes (n=1, 2, 3)
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Prof. Dr. Holger Braunschweig Dr. Alexander Damme Dr. Klaus Dück Dr. Marco Fuß Dr. Christian Hörl Dr. Thomas Kramer Dr. Ivo Krummenacher Dr. Thomas Kupfer Valerie Paprocki Christoph Schneider 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(42):14797-14803
We report the synthesis of [n]manganoarenophanes (n=1, 2) featuring boron, silicon, germanium, and tin as ansa‐bridging elements. Their preparation was achieved by salt‐elimination reactions of the dilithiated precursor [Mn(η5‐C5H4Li)(η6‐C6H5Li)]?pmdta (pmdta=N,N,N′,N′,N′′‐pentamethyldiethylenetriamine) with corresponding element dichlorides. Besides characterization by multinuclear NMR spectroscopy and elemental analysis, the identity of two single‐atom‐bridged derivatives, [Mn(η5‐C5H4)(η6‐C6H5)SntBu2] and [Mn(η5‐C5H4)(η6‐C6H5)SiPh2], could also be determined by X‐ray structural analysis. We investigated for the first time the reactivity of these ansa‐cyclopentadienyl–benzene manganese compounds. The reaction of the distannyl‐bridged complex [Mn(η5‐C5H4)(η6‐C6H5)Sn2tBu4] with elemental sulfur was shown to proceed through the expected oxidative addition of the Sn?Sn bond to give a triatomic ansa‐bridge. The investigation of the ring‐opening polymerization (ROP) capability of [Mn(η5‐C5H4)(η6‐C6H5)SntBu2] with [Pt(PEt3)3] showed that an unexpected, unselective insertion into the Cipso?Sn bonds of [Mn(η5‐C5H4)(η6‐C6H5)SntBu2] had occurred. 相似文献
2.
Diimido, Imido Oxo, Dioxo, and Imido Alkylidene Halfsandwich Compounds via Selective Hydrolysis and α—H Abstraction in Molybdenum(VI) and Tungsten(VI) Organyl Complexes Organometal imides [(η5‐C5R5)M(NR′)2Ph] (M = Mo, W, R = H, Me, R′ = Mes, tBu) 4 — 8 can be prepared by reaction of halfsandwich complexes [(η5‐C5R5)M(NR′)2Cl] with phenyl lithium in good yields. Starting from phenyl complexes 4 — 8 as well as from previously described methyl compounds [(η5‐C5Me5)M(NtBu)2Me] (M = Mo, W), reactions with aqueous HCl lead to imido(oxo) methyl and phenyl complexes [(η5‐C5Me5)M(NtBu)(O)(R)] M = Mo, R = Me ( 9 ), Ph ( 10 ); M = W, R = Ph ( 11 ) and dioxo complexes [(η5‐C5Me5)M(O)2(CH3)] M = Mo ( 12 ), M = W ( 13 ). Hydrolysis of organometal imides with conservation of M‐C σ and π bonds is in fact an attractive synthetic alternative for the synthesis of organometal oxides with respect to known strategies based on the oxidative decarbonylation of low valent alkyl CO and NO complexes. In a similar manner, protolysis of [(η5‐C5H5)W(NtBu)2(CH3)] and [(η5‐C5Me5)Mo(NtBu)2(CH3)] by HCl gas leads to [(η5‐C5H5)W(NtBu)Cl2(CH3)] 14 und [(η5‐C5Me5)Mo(NtBu)Cl2(CH3)] 15 with conservation of the M‐C bonds. The inert character of the relatively non‐polar M‐C σ bonds with respect to protolysis offers a strategy for the synthesis of methyl chloro complexes not accessible by partial methylation of [(η5‐C5R5)M(NR′)Cl3] with MeLi. As pure substances only trimethyl compounds [(η5‐C5R5)M(NtBu)(CH3)3] 16 ‐ 18 , M = Mo, W, R = H, Me, are isolated. Imido(benzylidene) complexes [(η5‐C5Me5)M(NtBu)(CHPh)(CH2Ph)] M = Mo ( 19 ), W ( 20 ) are generated by alkylation of [(η5‐C5Me5)M(NtBu)Cl3] with PhCH2MgCl via α‐H abstraction. Based on nmr data a trend of decreasing donor capability of the ligands [NtBu]2— > [O]2— > [CHR]2— ? 2 [CH3]— > 2 [Cl]— emerges. 相似文献
3.
The reaction of α,α′‐dimercapto‐o‐xylene (H2dmox) with different precursors such as SnMe2Cl2, [Ti(η5‐C5H5)2Cl2] and [Ti(η5‐C5H4Me)2Cl2] (1:1) in the presence of two equivalents of NEt3 yielded the complexes [SnMe2(dmox)] (1), [Ti(η5‐C5H5)2(dmox)] (2) and [Ti(η5‐C5H4Me)2(dmox)] (3), respectively. 1–3 have been characterized by spectroscopic methods; in addition, complex 3 has been determined by X‐ray diffraction studies. Furthermore, structural studies based on density functional theory calculations of 1 and 2 have been carried out. The cytotoxic activity of 1–3 was tested against the tumour cell lines human adenocarcinoma HeLa, human myelogenous leukaemia K562 and human malignant melanoma Fem‐x. The results of this study show a higher cytotoxicity of the tin(IV) complex (1) in comparison to their titanium(IV) counterparts (2 and 3) as well as an improvement in the cytotoxic activity of compounds 2 and 3 compared to their titanocene(IV) dichloride analogues [Ti(η5‐C5H5)2Cl2] and [Ti(η5‐C5H4Me)2Cl2]. In view of the relatively high cytotoxicity of compound 1, a detailed study on the effects of the in vitro treatment of cancer cell lines using this compound was carried out. Thus cell cycle experiments on all the studied cell lines treated with 1 show that this complex seems to cause disturbances in the G1 phase of HeLa, and in the G1 and G2/M phases of Fem‐x cell line, while almost no disturbances were observed in the cycle of K562 cells treated with 1. Finally, DNA laddering method showed that treatment of the HeLa and Fem‐x cell lines with IC90 doses of 1 resulted in the induction of apoptosis. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
4.
Chi Nguyen Thi Thanh Thong Pham Van Hai Le Thi Hong Luc Van Meervelt 《Acta Crystallographica. Section C, Structural Chemistry》2016,72(10):758-764
Crystallization experiments with the dinuclear chelate ring complex di‐μ‐chlorido‐bis[(η2‐2‐allyl‐4‐methoxy‐5‐{[(propan‐2‐yloxy)carbonyl]methoxy}phenyl‐κC1)platinum(II)], [Pt2(C15H19O4)2Cl2], containing a derivative of the natural compound eugenol as ligand, have been performed. Using five different sets of crystallization conditions resulted in four different complexes which can be further used as starting compounds for the synthesis of Pt complexes with promising anticancer activities. In the case of vapour diffusion with the binary chloroform–diethyl ether or methylene chloride–diethyl ether systems, no change of the molecular structure was observed. Using evaporation from acetonitrile (at room temperature), dimethylformamide (DMF, at 313 K) or dimethyl sulfoxide (DMSO, at 313 K), however, resulted in the displacement of a chloride ligand by the solvent, giving, respectively, the mononuclear complexes (acetonitrile‐κN)(η2‐2‐allyl‐4‐methoxy‐5‐{[(propan‐2‐yloxy)carbonyl]methoxy}phenyl‐κC1)chloridoplatinum(II) monohydrate, [Pt(C15H19O4)Cl(CH3CN)]·H2O, (η2‐2‐allyl‐4‐methoxy‐5‐{[(propan‐2‐yloxy)carbonyl]methoxy}phenyl‐κC1)chlorido(dimethylformamide‐κO)platinum(II), [Pt(C15H19O4)Cl(C2H7NO)], and (η2‐2‐allyl‐4‐methoxy‐5‐{[(propan‐2‐yloxy)carbonyl]methoxy}phenyl‐κC1)chlorido(dimethyl sulfoxide‐κS)platinum(II), determined as the analogue {η2‐2‐allyl‐4‐methoxy‐5‐[(ethoxycarbonyl)methoxy]phenyl‐κC1}chlorido(dimethyl sulfoxide‐κS)platinum(II), [Pt(C14H17O4)Cl(C2H6OS)]. The crystal structures confirm that acetonitrile interacts with the PtII atom via its N atom, while for DMSO, the S atom is the coordinating atom. For the replacement, the longest of the two Pt—Cl bonds is cleaved, leading to a cis position of the solvent ligand with respect to the allyl group. The crystal packing of the complexes is characterized by dimer formation via C—H…O and C—H…π interactions, but no π–π interactions are observed despite the presence of the aromatic ring. 相似文献
5.
2, 4‐Dimethylpenta‐1, 3‐diene and 2, 4‐Dimethylpentadienyl Complexes of Rhodium and Iridium The complexes [(η4‐C7H12)RhCl]2 ( 1 ) (C7H12 = 2, 4‐dimethylpenta‐1, 3‐diene) and [(η4‐C7H12)2IrCl] ( 2 ) were obtained by interaction of C7H12 with [(η2‐C2H4)2RhCl]2 and [(η2‐cyclooctene)2IrCl]2, respectively. The reaction of 1 or 2 with CpTl (Cp = η5‐C5H5) yields the compounds [CpM(η4‐C7H12)] ( 3a : M = Rh; 3b : M = Ir). The hydride abstraction at the pentadiene ligand of 3a , b with Ph3CBF4 proceeds differently depending on the solvent. In acetone or THF the “half‐open” metallocenium complexes [CpM(η5‐C7H11)]BF4 ( 4a : M = Rh; 4b : M = Ir) are obtained exclusively. In dichloromethane mixtures are produced which additionally contain the species [(η5‐C7H11)M(η5‐C5H4CPh3)]BF4 ( 5a : M = Rh; 5b : M = Ir) formed by electrophilic substitution at the Cp ring, as well as the η3‐2, 4‐dimethylpentenyl compound [(η3‐C7H13)Rh{η5‐C5H3(CPh3)2}]BF4 ( 6 ). By interaction of 2, 4‐dimethylpentadienyl potassium with 1 or 2 the complexes [(η4‐C7H12)M(η5‐C7H11)] ( 7a : M = Rh; 7b : M = Ir) are generated which show dynamic behaviour in solution; however, attempts to synthesize the “open” metallocenium cations [(η5‐C7H11)2M]+ by hydride abstraction from 7a , b failed. The new compounds were characterized by elemental analysis and spectroscopically, 4b and 5a also by X‐ray structure analysis. 相似文献
6.
Influence of Cyclopentadienyl Ring‐Tilt on Electron‐Transfer Reactions: Redox‐Induced Reactivity of Strained [2] and [3]Ruthenocenophanes
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Dr. Andrew D. Russell Prof. Joe B. Gilroy Prof. Kevin Lam Dr. Mairi F. Haddow Prof. Jeremy N. Harvey Prof. William E. Geiger Prof. Ian Manners 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(49):16216-16227
In contrast to ruthenocene [Ru(η5‐C5H5)2] and dimethylruthenocene [Ru(η5‐C5H4Me)2] ( 7 ), chemical oxidation of highly strained, ring‐tilted [2]ruthenocenophane [Ru(η5‐C5H4)2(CH2)2] ( 5 ) and slightly strained [3]ruthenocenophane [Ru(η5‐C5H4)2(CH2)3] ( 6 ) with cationic oxidants containing the non‐coordinating [B(C6F5)4]? anion was found to afford stable and isolable metal?metal bonded dicationic dimer salts [Ru(η5‐C5H4)2(CH2)2]2[B(C6F5)4]2 ( 8 ) and [Ru(η5‐C5H4)2(CH2)3]2[B(C6F5)4]2 ( 17 ), respectively. Cyclic voltammetry and DFT studies indicated that the oxidation potential, propensity for dimerization, and strength of the resulting Ru?Ru bond is strongly dependent on the degree of tilt present in 5 and 6 and thereby degree of exposure of the Ru center. Cleavage of the Ru?Ru bond in 8 was achieved through reaction with the radical source [(CH3)2NC(S)S?SC(S)N(CH3)2] (thiram), affording unusual dimer [(CH3)2NCS2Ru(η5‐C5H4)(η3‐C5H4)C2H4]2[B(C6F5)4]2 ( 9 ) through a haptotropic η5–η3 ring‐slippage followed by an apparent [2+2] cyclodimerization of the cyclopentadienyl ligand. Analogs of possible intermediates in the reaction pathway [C6H5ERu(η5‐C5H4)2C2H4][B(C6F5)4] [E=S ( 15 ) or Se ( 16 )] were synthesized through reaction of 8 with C6H5E?EC6H5 (E=S or Se). 相似文献
7.
Bernhard Miller Janina Altman Christian Leschke Walter Schunack Karlheinz Sünkel Jrg Knizek Heinrich Nth Wolfgang Beck 《无机化学与普通化学杂志》2000,626(4):978-984
Dinuclear Palladium(II), Platinum(II), and Iridium(III) Complexes of Bis[imidazol‐4‐yl]alkanes The reaction of bis(1,1′‐triphenylmethyl‐imidazol‐4‐yl) alkanes ((CH2)n bridged imidazoles L(CH2)nL, n = 3–6) with chloro bridged complexes [R3P(Cl)M(μ‐Cl)M(Cl)PR3] (M = Pd, Pt; R = Et, Pr, Bu) affords the dinuclear compounds [Cl2(R3P)M–L(CH2)nL–M(PR3)Cl2] 1 – 17 . The structures of [Cl2(Et3P)Pd–L(CH2)3L–Pd(PEt3)Cl2] ( 1 ), [Cl2(Bu3P)Pd–L(CH2)4L–Pd(PBu3)Cl2] ( 10 ), [Cl2(Et3P)Pd–L(CH2)5L–Pd(PEt3)Cl2] ( 3 ), [Cl2(Et3P)Pt–L(CH2)3L–Pt(PEt3)Cl2] ( 13 ) with trans Cl–M–Cl groups were determined by X‐ray diffraction. Similarly the complexes [Cl2(Cp*)Ir–L(CH2)nL–Ir(Cp*)Cl2] (n = 4–6) are obtained from [Cp*(Cl)Ir(μ‐Cl)2Ir(Cl)Cp*] and the methylene bridged bis(imidazoles). 相似文献
8.
Novel cyclohexyl‐based aminophosphine ligands and use of their Ru(II) complexes in transfer hydrogenation of ketones
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Cezmi Kayan Nermin Meriç Murat Aydemir Yusuf Selim Ocak Ak𝚤n Baysal Hamdi Temel 《应用有机金属化学》2014,28(2):127-133
Two new aminophosphines – furfuryl‐(N‐dicyclohexylphosphino)amine, [Cy2PNHCH2–C4H3O] ( 1 ) and thiophene‐(N‐dicyclohexylphosphino)amine, [Cy2PNHCH2–C4H3S] ( 2 ) – were prepared by the reaction of chlorodicyclohexylphosphine with furfurylamine and thiophene‐2‐methylamine. Reaction of the aminophosphines with [Ru(η6‐p‐cymene)(μ‐Cl)Cl]2 or [Ru(η6‐benzene)(μ‐Cl)Cl]2 gave corresponding complexes [Ru(Cy2PNHCH2–C4H3O)(η6‐p‐cymene)Cl2] ( 1a ), [Ru(Cy2PNHCH2–C4H3O)(η6‐benzene)Cl2] ( 1b ), [Ru(Cy2PNHCH2–C4H3S)(η6‐p‐cymene)Cl2] ( 2a ) and [Ru(Cy2PNHCH2–C4H3S)(η6‐benzene)Cl2] ( 2b ), respectively, which are suitable catalyst precursors for the transfer hydrogenation of ketones. In particular, [Ru(Cy2PNHCH2–C4H3S)(η6‐benzene)Cl2] acts as a good catalyst, giving the corresponding alcohols in 98–99% yield in 30 min at 82 °C (up to time of flight ≤ 588 h?1). Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
9.
Reijo Sillanp Jordi Llop Clara Vias Francecs Teixidor Raikko Kiveks 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(8):900-901
In the title compound, (η5‐2,5‐dimethylpyrrolyl)[(7,8,9,10,11‐η)‐7‐methyl‐7,8‐dicarba‐nido‐undecaborato]cobalt(III), [3‐Co{η5‐[2,5‐(CH3)2‐NC4H2]}‐1‐CH3‐1,2‐C2B9H10] or [Co(C3H13B9)(C6H8N)], the CoIII atom is sandwiched between the pentagonal faces of the pyrrolyl and dicarbollide ligands, resulting in a neutral molecule. The C—C distance in the dicarbollide cage is 1.649 (3) Å. 相似文献
10.
Monty Kessler Dr. Sven Hansen Christian Godemann Dr. Anke Spannenberg Dr. Torsten Beweries 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(20):6350-6357
The synthesis of a series of ansa‐titanocene dichlorides [Cp′2TiCl2] (Cp′=bridged η5‐tetramethylcyclopentadienyl) and the corresponding titanocene bis(trimethylsilyl)acetylene complexes [Cp′2Ti(η2‐Me3SiC2SiMe3)] is described. The ethanediyl‐bridged complexes [C2H4(C5Me4)2TiCl2] ( 2 ‐Cl2) and [C2H4(C5Me4)2Ti(η2‐Me3SiC2SiMe3)] ( 2‐ btmsa; btmsa=η2‐Me3SiC2SiMe3) can be obtained from the hitherto unknown calcocenophane complex [C2H4(C5Me4)2Ca(THF)2] ( 1 ). Furthermore, a heterodiatomic bridging unit containing both, a dimethylsilyl and a methylene group was introduced to yield the ansa‐titanocene dichloride [Me2SiCH2(C5Me4)2TiCl2] ( 3 ‐Cl2) and the bis(trimethylsilyl)acetylene complex [Me2SiCH2(C5Me4)2Ti(η2‐Me3SiC2SiMe3)] ( 3 ‐btmsa). Besides, tetramethyldisilyl‐ and dimethylsilyl‐bridged metallocene complexes (structural motif 4 and 5 , respectively) were prepared. All ansa‐titanocene alkyne complexes were reacted with stoichiometric amounts of water; the hydrolysis products were isolated as model complexes for the investigation of the elemental steps of overall water splitting. Compounds 1 , 2 ‐btmsa, 2 ‐(OH)2, 3 ‐Cl2, 3 ‐btmsa, 4 ‐(OH)2, 3 ‐alkenyl and 5 ‐alkenyl were characterised by X‐ray diffraction analysis. 相似文献
11.
Dominique Robert Dr. Elise Abinet Dipl.‐Chem. Thomas P. Spaniol Dr. Jun Okuda Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(44):11937-11947
Monocationic bis‐allyl complexes [Ln(η3‐C3H5)2(thf)3]+[B(C6X5)4]? (Ln=Y, La, Nd; X=H, F) and dicationic mono‐allyl complexes of yttrium and the early lanthanides [Ln(η3‐C3H5)(thf)6]2+[BPh4]2? (Ln=La, Nd) were prepared by protonolysis of the tris‐allyl complexes [Ln(η3‐C3H5)3(diox)] (Ln=Y, La, Ce, Pr, Nd, Sm; diox=1,4‐dioxane) isolated as a 1,4‐dioxane‐bridged dimer (Ln=Ce) or THF adducts [Ln(η3‐C3H5)3(thf)2] (Ln=Ce, Pr). Allyl abstraction from the neutral tris‐allyl complex by a Lewis acid, ER3 (Al(CH2SiMe3)3, BPh3) gave the ion pair [Ln(η3‐C3H5)2(thf)3]+[ER3(η1‐CH2CH?CH2)]? (Ln=Y, La; ER3=Al(CH2SiMe3)3, BPh3). Benzophenone inserts into the La? Callyl bond of [La(η3‐C3H5)2(thf)3]+[BPh4]? to form the alkoxy complex [La{OCPh2(CH2CH?CH2)}2(thf)3]+[BPh4]?. The monocationic half‐sandwich complexes [Ln(η5‐C5Me4SiMe3)(η3‐C3H5)(thf)2]+[B(C6X5)4]? (Ln=Y, La; X=H, F) were synthesized from the neutral precursors [Ln(η5‐C5Me4SiMe3)(η3‐C3H5)2(thf)] by protonolysis. For 1,3‐butadiene polymerization catalysis, the yttrium‐based systems were more active than the corresponding lanthanum or neodymium homologues, giving polybutadiene with approximately 90 % 1,4‐cis stereoselectivity. 相似文献
12.
Holger Braunschweig Frank M. Breitling Katharina Kraft Mario Kraft Fabian Seeler Sascha Stellwag Krzysztof Radacki 《无机化学与普通化学杂志》2006,632(2):269-278
A wide range of potential ligand precursors and related compounds have been synthesized from ferrocenyldibromoborane and ferrocenylenebis(dibromoborane) via salt elimination reactions. These comprise ligand precursors suitable for the preparation of (i) ansa‐metallocenes such as [FcB(η1‐C5H5)2] ( 2 ), [FcB(1‐C9H7)2] ( 3 ), [FcB(3‐C9H7)2] ( 4 ) and [1,1′‐fc{B(3‐C9H7)2}2] ( 11 ), (ii) constrained geometry complexes such as [FcB(1‐C9H7)N(H)Ph] ( 7 ) and [FcB(3‐C9H7)N(H)Ph] ( 8 ), (iii) ansa‐diamido complexes such as [FcB(N(H)Ph)2] ( 9 ) as well as (iv) the related compounds [FcB(Br)N(H)tBu] ( 5 ), [FcB(Br)N(H)Ph] ( 6 ), [1,1′‐fc{B(Br)N(SiMe3)2}2] ( 12 ) and [1,1′‐fc{B(Br)NiPr2}2] ( 13 ) (Fc = ferrocenyl, fc = ferrocenylene, C5H5 = cyclopentadienyl, C9H7 = indenyl). All new compounds have been characterised by multinuclear NMR spectroscopic techniques and in the case of 7 and 12 by X‐ray diffraction methods. 相似文献
13.
D. Carmona S. Chaloupka J. Jans R. Thouvenot L.M. Venanzi 《Journal of organometallic chemistry》1984,275(2):303-313
The preparations of cis- and trans-[PtH(C6Cl5)(PEt3)2] by thermal decomposition of cis- and trans-[Pt(OCHO)(C6Cl5)(PEt3)2], respectively, are reported. Also described are cis- and trans-[Pt(SnCl3)(C6Cl5)(PEt3)2], obtained by treating SnCl2 with cis- and trans-[PtCl(C6,Cl5)(PEt3)2], respectively. It is shown that while trans- [PtH(C6Cl5)(PEt3)2] does not form hydride-bridged complexes in the presence of trans-(PtH(MeOH)(PEt3)2]+, the corresponding complex trans-[PtH(C6)(PEt3)2] reacts with the same solvento complex, in methanol, giving labile [(PEt3)2HPt(-μH)Pt(C6F5)(PEt3)2]+. 相似文献
14.
Ramn Macías Simon A. Barrett Jonathan Bould Udo Drfler Josef Holub John D. Kennedy Mark Thornton‐Pett Bohumil tíbr 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(5):520-522
Neutral 8‐(5‐iodo‐n‐pentyl)‐3‐(η5‐pentamethylcyclopentadienyl)‐arachno‐3‐rhoda‐7,8‐dithiaundecaborane, [Rh(C5H19B8IS2)(C10H15)], obtained from the [arachno‐7,8‐S2B9H10]? anion by treatment with I(CH2)5I followed by [Rh(C5Me5)Cl2]2 and N,N,N′,N′‐tetramethyl‐1,8‐diaminonaphthalene, has the 11‐vertex cluster geometry of [arachno‐7,8‐S2B9H10]?, but with an {Rh(C5Me5)} unit in the 3‐position instead of a {BH} unit, and with a –(CH2)5I chain attached exo to an S atom. 相似文献
15.
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
16.
Sigma‐ versus Pi‐Coordination in Bis‐indenyl‐ and Bis‐2‐methallyl Imido Complexes of Hexavalent Molybdenum and Tungsten: DF‐Calculations and Crystal Structure Analysis Bis‐indenyl and bis‐2‐methallyl imido complexes [(C9H7)2M(NR)2] (M = Mo, W; R = tert‐butyl, mesityl) 1 — 4 and [(H3C‐C3H4)2M(NtBu)2] (M = Mo, W) 6 , 7 have been prepared starting from [Mo(NtBu)2Cl2] or [M(NR)2Cl2L2] (M = W, R = tBu, L = py; M = Mo, W, R = Mes, L2 = dme) and indenyl lithium or 2‐methallyl magnesium bromide, respectively. According to spectroscopic data and the crystal structure of 4 there are two different coordination modes of the indenyl ligands, [(η3‐C9H7)M(NR)2(η1‐C9H7)], in solution as well as in the solid state. These compounds show fluxional rearrangements in solution, namely σ, π‐exchange of η1‐ and η3‐coordinated ligands. Similar behavior has been observed for the 2‐methallyl complexes 6 and 7 in solution. In agreement with experimental observations, DF calculations on models of 6 strongly suggest a (σ+π)‐coordination mode of the η3‐coordinated ligand. 相似文献
17.
Kishie Noguchi Takashi Tamura Hidetaka Yuge Takeshi Ken Miyamoto 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(2):171-173
In two linkage isomers, bis[1,3‐dimethyl‐2,4,6(1H,3H,5H)‐pyrimidinetrionato]‐C5,O4‐(ethylenediamine‐N,N′)platinum(II), [Pt(C6H7N2O3)2(C2H8N2)], (I), and bis[1,3‐dimethyl‐2,4,6(1H,3H,5H)‐pyrimidinetrionato‐C5](ethylenediamine‐N,N′)platinum(II) dihydrate, [Pt(C6H7N2O3)2(C2H8N2)]·2H2O, (II), crystallized from the same aqueous solution containing [Pt(en)(OH)2] and 1,3‐dimethylbarbituric acid (Hdmbarb) in a 1:2 molar ratio, a pair of monodentate dmbarb? anions coordinate to the Pt atom at tetrahedral C atoms for (II), while one dmbarb? anion coordinates at the carbon and the other at a deprotonated enol oxygen for (I). The Pt—C distances in (I) and (II) are comparable: 2.112 (4) Å for (I), and 2.114 (4) and 2.117 (4) Å for (II). 相似文献
18.
Different Complexation Behavior of P‐Functionalized Ferrocene Derivatives Towards SnCl2, SnCl4 and SnPh2Cl2: Auto‐ionization and Redox‐Type Reactions
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Dipl.‐Chem. Matthias Gawron Dr. Christina Dietz Michael Lutter Dr. Andrew Duthie Prof. Dr. Viatcheslav Jouikov Prof. Dr. Klaus Jurkschat 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(46):16609-16622
The novel phosphonyl‐substituted ferrocene derivatives [Fe(η5‐Cp)(η5‐C5H3{P(O)(O‐iPr)2}2‐1,2)] ( Fc1,2 ) and [Fe{η5‐C5H4P(O)(O‐iPr)2}2] ( Fc1,1′ ) react with SnCl2, SnCl4, and SnPh2Cl2, giving the corresponding complexes [(Fc1,2)2SnCl][SnCl3] ( 1 ), [{(Fc1,1′)SnCl2}n] ( 2 ), [(Fc1,1′)SnCl4] ( 3 ), [{(Fc1,1′)SnPh2Cl2}n] ( 4 ), and [(Fc1,2)SnCl4] ( 5 ), respectively. The compounds are characterized by elemental analyses, 1H, 13C, 31P, 119Sn NMR and IR spectroscopy, 31P and 119Sn CP‐MAS NMR spectroscopy, cyclovoltammetry, electrospray ionization mass spectrometry, and single‐crystal as well as powder X‐ray diffraction analyses. The experimental work is accompanied by DFT calculations, which help to shed light on the origin for the different reaction behavior of Fc1,1′ and Fc1,2 towards tin(II) chloride. 相似文献
19.
Karel Mach Jií Kubita Ivana Císaov Petr tpni
ka 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(2):m116-m118
Reacting stoichiometric amounts of 1‐(diphenylphosphino)ferrocenecarboxylic acid and [Ti(η5‐C5HMe4)2(η2‐Me3SiC[triple‐bond]CSiMe3)] produced the title carboxylatotitanocene complex, [{μ‐1κ2O,O′:2(η5)‐C5H4CO2}{2(η5)‐C5H4P(C6H5)2}{1(η5)‐C5H(CH3)4}2FeIITiIII] or [FeTi(C9H13)2(C6H4O2)(C17H14P)]. The angle subtended by the Ti/O/O′ plane, where O and O′ are the donor atoms of the κ2‐carboxylate group, and the plane of the carboxyl‐substituted ferrocene cyclopentadienyl is 24.93 (6)°. 相似文献
20.
David E. Herbert Ulrich F. J. Mayer Joe B. Gilroy Dr. María J. López‐Gómez Alan J. Lough Dr. Jonathan P. H. Charmant Dr. Ian Manners Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(45):12234-12246
The ring‐opening polymerization (ROP) behavior of a variety of substituted 1,1′‐ethylenylferrocenes, or dicarba[2]ferrocenophanes, is reported. The electronic absorption spectra and tilted solid‐state structures of the monomers rac‐[Fe(η5‐C5H4)2(CHiPr)2] ( 7 ), [Fe(η5‐C5H4)2(C(H)MeCH2)] ( 8 ), and rac‐[Fe(η5‐C5H4)2(CHPh)2] ( 9 ) are consistent with the presence of substantial ring strain, which was exploited to synthesize soluble, well‐defined polyferrocenylethylenes (PFEs) [Fe(η5‐C5H4)2(C(H)MeCH2)]n ( 12 ) and [Fe(η5‐C5H4)2(CHPh)2]n ( 13 ) through photocontrolled ROP. Polymer chain lengths could be controlled by the monomer‐to‐initiator ratio up to about 50 repeat units and, consistent with the “living” nature of the polymerizations, sequential block copolymerization with a sila[1]ferrocenophane led to polyferrocenylethylene–polyferrocenylsilane (PFE‐b‐PFS) block copolymers ( 14 and 15 ). PFE polymers 12 and 13 showed two reversible oxidation waves, indicative of appreciable Fe???Fe interactions along the polymer backbone. The diblock copolymers were characterized by NMR spectroscopy, GPC analysis, and cyclic voltammetry. 相似文献