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1.
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
2.
Christian P. Sindlinger Paul Niklas Ruth 《Angewandte Chemie (International ed. in English)》2019,58(42):15051-15056
The pentaaryl borole (Ph*C)4BXylF [Ph*=3,5‐tBu2(C6H3); XylF=3,5‐(CF3)2(C6H3)] reacts with low‐valent Group 13 precursors AlCp* and GaCp* by two divergent routes. In the case of [AlCp*]4, the borole reacts as an oxidising agent and accepts two electrons. Structural, spectroscopic, and computational analysis of the resulting unprecedented neutral η5‐Cp*,η5‐[(Ph*C)4BXylF] complex of AlIII revealed a strong, ionic bonding interaction. The formation of the heteroleptic borole‐cyclopentadienyl “aluminocene” leads to significant changes in the 13C NMR chemical shifts within the borole unit. In the case of the less‐reductive GaCp*, borole (Ph*C)4BXylF reacts as a Lewis acid to form a dynamic adduct with a dative 2‐center‐2‐electron Ga?B bond. The Lewis adduct was also studied structurally, spectroscopically, and computationally. 相似文献
3.
Philipp Dabringhaus Silja Zedlitz Luisa Giarrana David Scheschkewitz Ingo Krossing 《Angewandte Chemie (International ed. in English)》2023,62(8):e202215170
Schnöckel's [(AlCp*)4] and Jutzi's [SiCp*][B(C6F5)4] (Cp*=C5Me5) are landmarks in modern main-group chemistry with diverse applications in synthesis and catalysis. Despite the isoelectronic relationship between the AlCp* and the [SiCp*]+ fragments, their mutual reactivity is hitherto unknown. Here, we report on their reaction giving the complex salts [Cp*Si(AlCp*)3][WCA] ([WCA]−=[Al(ORF)4]− and [F{Al(ORF)3}2]−; RF=C(CF3)3). The tetrahedral [SiAl3]+ core not only represents a rare example of a low-valent silicon-doped aluminium-cluster, but also—due to its facile accessibility and high stability—provides a convenient preparative entry towards low-valent Si−Al clusters in general. For example, an elusive binuclear [Si2(AlCp*)5]2+ with extremely short Al−Si bonds and a high negative partial charge at the Si atoms was structurally characterised and its bonding situation analysed by DFT. Crystals of the isostructural [Ge2(AlCp*)5]2+ dication were also obtained and represent the first mixed Al−Ge cluster. 相似文献
4.
M. T. Duarte V. Gama S. Rabaa I. C. Santos 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(7):m278-m280
The title compound, [Fe(C10H15)2][Ni(C3OS4)2]·C4H8O or [Fe(Cp*)2][Ni(dmio)2]·THF, where [Fe(Cp*)2]+ is the decamethylferrocenium cation, dmio is the 2‐oxo‐1,3‐dithiole‐4,5‐dithiolate dianion and THF is tetrahydrofuran, crystallizes with two independent half‐anion units [one Ni atom is at the centre of symmetry (, , 0) and the other is at the centre of symmetry (, 0, )], one cation unit (located in a general position) and one THF solvent molecule in the asymmetric unit. The crystal structure consists of two‐dimensional layers composed of parallel mixed chains, where pairs of cations alternate with single anions. These layers are separated by sheets of anions and THF molecules. 相似文献
5.
Chemistry of N,S‐Heterocyclic Carbene and Metallaboratrane Complexes: A New η3‐BCC‐Borataallyl Complex 下载免费PDF全文
Dr. Dipak Kumar Roy Anangsha De Subhankar Panda Dr. Babu Varghese Prof. Sundargopal Ghosh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(39):13732-13738
A high‐yielding synthetic route for the preparation of group 9 metallaboratrane complexes [Cp*MBH(L)2], 1 and 2 ( 1 , M=Rh, 2 , M=Ir; L=C7H4NS2) has been developed using [{Cp*MCl2}2] as precursor. This method also permitted the synthesis of an Rh–N,S‐heterocyclic carbene complex, [(Cp*Rh)(L2)(1‐benzothiazol‐2‐ylidene)] ( 3 ; L=C7H4NS2) in good yield. The reaction of compound 3 with neutral borane reagents led to the isolation of a novel borataallyl complex [Cp*Rh(L)2B{CH2C(CO2Me)}] ( 4 ; L=C7H4NS2). Compound 4 features a rare η3‐interaction between rhodium and the B‐C‐C unit of a vinylborane moiety. Furthermore, with the objective of generating metallaboratranes of other early and late transition metals through a transmetallation approach, reactions of rhoda‐ and irida‐boratrane complexes with metal carbonyl compounds were carried out. Although the objective of isolating such complexes was not achieved, several interesting mixed‐metal complexes [{Cp*Rh}{Re(CO)3}(C7H4NS2)3] ( 5 ), [Cp*Rh{Fe2(CO)6}(μ‐CO)S] ( 6 ), and [Cp*RhBH(L)2W(CO)5] ( 7 ; L=C7H4NS2) have been isolated. All of the new compounds have been characterized in solution by mass spectrometry, IR spectroscopy, and 1H, 11B, and 13C NMR spectroscopies, and the structural types of 4 – 7 have been unequivocally established by crystallographic analysis. 相似文献
6.
Syntheses, Structure and Reactivity of η3‐1,2‐Diphosphaallyl Complexes and [{(η5‐C5H5)(CO)2W–Co(CO)3}{μ‐AsCH(SiMe3)2}(μ‐CO)] Reaction of ClP=C(SiMe2iPr)2 ( 3 ) with Na[Mo(CO)3(η5‐C5H5)] afforded the phosphavinylidene complex [(η5‐C5H5)(CO)2Mo=P=C(SiMe2iPr)2] ( 4 ) which in situ was converted into the η1‐1,2‐diphosphaallyl complex [η5‐(C5H5)(CO)2Mo{η3‐tBuPPC(SiMe2iPr)2] ( 6 ) by treatment with the phosphaalkene tBuP=C(NMe2)2. The chloroarsanyl complexes [(η5‐C5H5)(CO)3M–As(Cl)CH(SiMe3)2] [where M = Mo ( 9 ); M = W ( 10 )] resulted from the reaction of Na[M(CO)3(η5‐C5H5)] (M = Mo, W) with Cl2AsCH(SiMe3)2. The tungsten derivative 10 and Na[Co(CO)4] underwent reaction to give the dinuclear μ‐arsinidene complex [(η5‐C5H5)(CO)2W–Co(CO)3{μ‐AsCH(SiMe3)2}(μ‐CO)] ( 11 ). Treatment of [(η5‐C5H5)(CO)2Mo{η3‐tBuPPC(SiMe3)2}] ( 1 ) with an equimolar amount of ethereal HBF4 gave rise to a 85/15 mixture of the saline complexes [(η5‐C5H5)(CO)2Mo{η2‐tBu(H)P–P(F)CH(SiMe3)2}]BF4 ( 18 ) and [Cp(CO)2Mo{F2PCH(SiMe3)2}(tBuPH2)]BF4 ( 19 ) by HF‐addition to the PC bond of the η3‐diphosphaallyl ligand and subsequent protonation ( 18 ) and/or scission of the PP bond by the acid ( 19 ). Consistently 19 was the sole product when 1 was allowed to react with an excess of ethereal HBF4. The products 6 , 9 , 10 , 11 , 18 and 19 were characterized by means of spectroscopy (IR, 1H‐, 13C{1H}‐, 31P{1H}‐NMR, MS). Moreover, the molecular structures of 6 , 11 and 18 were determined by X‐ray diffraction analysis. 相似文献
7.
The reactions of Cp*M(PMe3)Cl2 (M = Rh ( 1a ), Ir ( 1b )) with (NEt4)2[WS4] led to the heterodimetallic sulfido‐bridged complexes Cp*M(PMe3)[(μ‐S)2WS2] (M = Rh ( 2a ), Ir ( 2b )), whereas the dimers [Cp*MCl(μ‐Cl)]2 (M = Rh ( 4a ), Ir ( 4b )) reacted with (NEt4)2[WS4) to give the known trinuclear compounds [Cp*M(Cl)]2(μ‐WS4) (M = Rh ( 5a ), Ir ( 5b )). Hydrolysis of the terminal W=S bonds converts 2a, b into Cp*M(PMe3)[(μ‐S)2WO2] (M = Rh ( 3a ), Ir ( 3b )). Salts of a heterodimetallic anion, A[CpMo(I)(NO)(WS4)] ( 6 ) (A+ = NEt4+, NPh4+) were obtained by reactions of [CpMo(NO)I2]2 with tetrathiotungstates, A2[WS4]. The complexes were characterized by IR and NMR (1H, 13C, 31P) spectroscopy, and the X‐ray crystallographic structure of Cp*Rh(PMe3)[(μ‐S)2WS2] ( 2a ) has been determined. The bond lengths and angles in the coordinations spheres of Rh and W in 2a (Rh···W 288.5(1) pm) are compared with related complexes containing terminal [WS42—] chelate ligands. 相似文献
8.
Pavel A. Dub Natalia V. Belkova Dr. Oleg A. Filippov Dr. Jean‐Claude Daran Dr. Lina M. Epstein Prof. Agustí Lledós Prof. Elena S. Shubina Prof. Rinaldo Poli Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(1):189-201
Low‐temperature (200 K) protonation of [Mo(CO)(Cp*)H(PMe3)2] ( 1 ) by Et2O ? HBF4 gives a different result depending on a subtle solvent change: The dihydrogen complex [Mo(CO)(Cp*)(η2‐H2)(PMe3)2]+ ( 2 ) is obtained in THF, whereas the tautomeric classical dihydride [Mo(CO)(Cp*)(H)2(PMe3)2]+ ( 3 ) is the only observable product in dichloromethane. Both products were fully characterised (νCO IR; 1H, 31P, 13C NMR spectroscopies) at low temperature; they lose H2 upon warming to 230 K at approximately the same rate (ca. 10?3 s?1), with no detection of the non‐classical form in CD2Cl2, to generate [Mo(CO)(Cp*)(FBF3)(PMe3)2] ( 4 ). The latter also slowly decomposes at ambient temperature. One of the decomposition products was crystallised and identified by X‐ray crystallography as [Mo(CO)(Cp*)(FH???FBF3)(PMe3)2] ( 5 ), which features a neutral HF ligand coordinated to the transition metal through the F atom and to the BF4? anion through a hydrogen bond. The reason for the switch in relative stability between 2 and 3 was probed by DFT calculations based on the B3LYP and M05‐2X functionals, with inclusion of anion and solvent effects by the conductor‐like polarisable continuum model and by explicit consideration of the solvent molecules. Calculations at the MP4(SDQ) and CCSD(T) levels were also carried out for calibration. The calculations reveal the key role of non‐covalent anion–solvent interactions, which modulate the anion–cation interaction ultimately altering the energetic balance between the two isomeric forms. 相似文献
9.
Jürgen Pahl Tom E. Stennett Michel Volland Dirk M. Guldi Sjoerd Harder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(8):2025-2034
[(BDI)Mg+][B(C6F5)4−] ( 1 ; BDI=CH[C(CH3)NDipp]2; Dipp=2,6-diisopropylphenyl) was prepared by reaction of (BDI)MgnPr with [Ph3C+][B(C6F5)4−]. Addition of 3-hexyne gave [(BDI)Mg+ ⋅ (EtC≡CEt)][B(C6F5)4−]. Single-crystal X-ray analysis, NMR investigations, Raman spectra, and DFT calculations indicate a significant Mg-alkyne interaction. Addition of the terminal alkynes PhC≡CH or Me3SiC≡CH led to alkyne deprotonation by the BDI ligand to give [(BDI-H)Mg+(C≡CPh)]2 ⋅ 2 [B(C6F5)4−] ( 2 , 70 %) and [(BDI-H)Mg+(C≡CSiMe3)]2 ⋅ 2 [B(C6F5)4−] ( 3 , 63 %). Addition of internal alkynes PhC≡CPh or PhC≡CMe led to [4+2] cycloadditions with the BDI ligand to give {Mg+C(Ph)=C(Ph)C[C(Me)=NDipp]2}2 ⋅ 2 [B(C6F5)4−] ( 4 , 53 %) and {Mg+C(Ph)=C(Me)C[C(Me)=NDipp]2}2 ⋅ 2 [B(C6F5)4−] ( 5 , 73 %), in which the Mg center is N,N,C-chelated. The (BDI)Mg+ cation can be viewed as an intramolecular frustrated Lewis pair (FLP) with a Lewis acidic site (Mg) and a Lewis (or Brønsted) basic site (BDI). Reaction of [(BDI)Mg+][B(C6F5)4−] ( 1 ) with a range of phosphines varying in bulk and donor strength generated [(BDI)Mg+ ⋅ PPh3][B(C6F5)4−] ( 6 ), [(BDI)Mg+ ⋅ PCy3][B(C6F5)4−] ( 7 ), and [(BDI)Mg+ ⋅ PtBu3][B(C6F5)4−] ( 8 ). The bulkier phosphine PMes3 (Mes=mesityl) did not show any interaction. Combinations of [(BDI)Mg+][B(C6F5)4−] and phosphines did not result in addition to the triple bond in 3-hexyne, but during the screening process it was discovered that the cationic magnesium complex catalyzes the hydrophosphination of PhC≡CH with HPPh2, for which an FLP-type mechanism is tentatively proposed. 相似文献
10.
L. Weber S. Uthmann S. Kleinebekel H.‐G. Stammler A. Stammler B. Neumann 《无机化学与普通化学杂志》2000,626(8):1831-1836
Syntheses and Structures of η1‐Phosphaallyl, η1‐Arsaallyl, and η1‐Stibaallyl Iron Complexes [(η5‐C5Me5)(CO)2Fe–E(SiMe3)C(OSiMe3)=CPh2] (E = P, As, Sb) The reaction of equimolar amounts of [(η5‐C5Me5)(CO)2Fe–E(SiMe3)2] ( 1 a : E = P; 1 b : As; 1 c : Sb) and diphenylketene afforded the η1‐phosphaallyl‐, η1‐arsaallyl‐, and η1‐stibaallyl complexes [(η5‐C5Me5)(CO)2Fe–E(SiMe3)C(OSiMe3)=CPh2] ( 2 a : E = P; 2 b : As; 2 c : Sb). The molecular structures of 2 b and 2 c were elucidated by single crystal X‐ray analyses. 相似文献
11.
Jian-Long Xia Wei-Cheng Xiong Gang Chen Guang-Ao Yu Shan Jin Sheng-Hua Liu 《Transition Metal Chemistry》2009,34(4):389-393
Abstract Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H2O)(NBD)][BF4] (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2. The reaction of [Cp*Ru(H2O)(NBD)][BF4] with 1,4-diphenylbutadiyne generates the unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C9H8–Ph in addition to the organometallic compound [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4]. [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BPh4]2 is generated after the reaction of compound [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2 with Na[BPh4]. The structure of this compound was confirmed by X-ray diffraction. A possible approach to form Ph–C≡C–C9H8–Ph and [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4] is suggested.
Graphical Abstract Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H2O)(NBD)]BF4 (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2. The reaction of [Cp*Ru(H2O)(NBD)][BF4] with 1,4-diphenylbutadiyne simply generates unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C9H8–Ph in addition to the organometallic compound [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4]. [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BPh4]2 is generated after the reaction of compound [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2 with Na[BPh4]. The structure of this compound was confirmed by X-ray diffraction. And the possible approach to form Ph–C≡C–C9H8–Ph and [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4] was suggested.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
12.
The bis‐phosphonio‐benzo[c]phospholide tetraphenylborate 4 [BPh4] reacts with CpCo(C2H4)2 to form a chelate complex [Co(η5–Cp)(κ2P,η2(P=C) –4 )][BPh4] ( 6 [BPh4]) which was characterized by means of spectroscopic techniques and a single crystal X‐ray diffraction study. The observed η2(π)‐coordination of the benzophospholide moiety in the cation 6 is highly unusual for aromatic phosphorus heterocycles. The structural data suggest a pronounced coordination‐induced localization of π‐electrons in the condensed ring system. 相似文献
13.
Ross F. Koby Alicia M. Doerr Nicholas R. Rightmire Nathan D. Schley Brian K. Long Timothy P. Hanusa 《Angewandte Chemie (International ed. in English)》2020,59(24):9542-9548
Milling two equivalents of K[1,3‐(SiMe3)2C3H3] (=K[A′]) with MgX2 (X=Cl, Br) produces the allyl complex [K2MgA′4] ( 1 ). Crystals grown from toluene are of the solvated species [((η6‐tol)K)2MgA′4] ([ 1 ?2(tol)]), a trimetallic monomer with both bridging and terminal (η1) allyl ligands. When recrystallized from hexanes, the unsolvated 1 forms a 2D coordination polymer, in which the Mg is surrounded by three allyl ligands. The C?C bond lengths differ by only 0.028 Å, indicating virtually complete electron delocalization. This is an unprecedented coordination mode for an allyl ligand bound to Mg. DFT calculations indicate that in isolation, an η3‐allyl configuration on Mg is energetically preferred over the η1‐ (σ‐bonded) arrangement, but the Mg must be in a low coordination environment for it to be experimentally realized. Methyl methacrylate is effectively polymerized by 1 , with activities that are comparable to K[A′] and greater than the homometallic magnesium complex [{MgA′2}2]. 相似文献
14.
Wannida Apisuk Naohiro Suzuki Hyun Joon Kim Dong Hyun Kim Boonyarach Kitiyanan Kotohiro Nomura 《Journal of polymer science. Part A, Polymer chemistry》2013,51(12):2565-2574
Aryloxo‐modified half‐titanocenes, Cp′TiCl2(O‐2,6‐iPr2C6H3) [Cp′ = Cp* ( 1 ), tBuC5H4 ( 2 )], catalyze terpolymerization of ethylene and styrene with α‐olefin (1‐hexene and 1‐decene) efficiently in the presence of cocatalyst, affording high‐molecular‐weight polymers with unimodal distributions (compositions). Efficient comonomer incorporations have been achieved by these catalysts. The content of each comonomer (α‐olefin, styrene, etc.) could be controlled by varying the comonomer concentration charged, and resonances ascribed to styrene and α‐olefin repeated insertion were negligible. The terpolymerization with p‐methylstyrene (p‐MS) in place of styrene also proceeded in the presence of [PhN(H)Me2][B(C6F5)4] and AliBu3 cocatalyst, and p‐MS was incorporated in an efficient matter, affording high‐molecular‐weight polymers with uniform molecular weight distributions. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2565–2574 相似文献
15.
The Potential of the Diarsene Complex [(C5H5)2Mo2(CO)4(μ,η2-As2)] as a Connector Between Silver Ions
Dr. Mehdi Elsayed Moussa Jana Schiller Dr. Eugenia Peresypkina Dr. Michael Seidl Dr. Gábor Balázs Pavel Shelyganov Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(63):14315-14319
The reaction of the organometallic diarsene complex [Cp2Mo2(CO)4(μ,η2-As2)] ( B ) (Cp = C5H5) with Ag[FAl{OC6F10(C6F5)}3] (Ag[FAl]) and Ag[Al{OC(CF3)3}4] (Ag[TEF]), respectively, yields three unprecedented supramolecular assemblies [(η2- B )4Ag2][FAl]2 ( 4 ), [(μ,η1:η2- B )3(η2- B )2Ag3][TEF]3 ( 5 ) and [(μ,η1:η2- B )4Ag3][TEF]3 ( 6 ). These products are only composed of the complexes B and AgI. Moreover, compounds 5 and 6 are the only supramolecular assemblies featuring B as a linking unit, and the first examples of [AgI]3 units stabilized by organometallic bichelating ligands. According to DFT calculations, complex B coordinates to metal centers through both the As lone pair and the As−As σ-bond thus showing this unique feature of this diarsene ligand. 相似文献
16.
Unexpected Reduction of [Cp*TaCl4(PH2R)] (R = But, Cy, Ad, Ph, 2,4,6‐Me3C6H2; Cp* = C5Me5) by Reaction with DBU – Molecular Structure of [(DBU)H][Cp*TaCl4] (DBU = 1,8‐diazabicyclo[5.4.0]undec‐7‐ene) [Cp*TaCl4(PH2R)] (R = But, Cy, Ad, Ph, 2,4,6‐Me3C6H2 (Mes); Cp* = C5Me5) react with DBU in an internal redox reaction with formation of [(DBU)H][Cp*TaCl4] ( 1 ) (DBU = 1,8‐diazabicyclo[5.4.0]undec‐7‐ene) and the corresponding diphosphane (P2H2R2) or decomposition products thereof. 1 was characterised spectroscopically and by crystal structure determination. In the solid state, hydrogen bonding between the (DBU)H cation and one chloro ligand of the anion is observed. 相似文献
17.
Matthias Stender Hannes Oesen Steffen Blaurock Evamarie Hey‐Hawkins 《无机化学与普通化学杂志》2001,627(5):980-984
Synthesis and Molecular Structure of [{Cp′(μ‐η1 : η5‐C5H3Me)Mo(μ‐AlRH)}2] (Cp′ = C5H4Me, R = iBu, Et) [Cp′2MoH2] reacts with HAlR2 to give [{Cp′(μ‐η1 : η5‐C5H3Me)Mo(μ‐AlRH)}2] (Cp′ = C5H4Me, R = iBu ( 1 ), Et ( 2 )). Crystal structure determinations were carried out on [Cp′2MoH2] and 1 . 1 exhibits a direct Mo–Al bond (2.636(2) Å). 相似文献
18.
《Journal of organometallic chemistry》1986,303(1):C8-C12
Li2[(C5Me4)2CH2] (III), the dilithium salt of the novel permethylated ring-connected [(C5Me4)2CH2]2− dianion, has been prepared from C5Me4H2 (I) via (C5Me4H)2CH2 (II) and subsequent reaction with n-BuLi. III reacts with [Rh(C2H4)(PMe3)Cl]2 to give the dinuclear complex [(C5Me4)2CH2][Rh(C2H4)PMe3]2 (IV) from which on methylation the compounds {[(C5Me4)2CH2][RhCH3(C2H4)PMe3]2} (PF6)2 (V) and [(C5Me4)2CH2][RhCH3(PMe3)I]2 (VI) are obtained. Treatment of IV with excess trifluoroacetic acid leads to the formation of [(C5Me4)2CH2](Rh(PMe3)(OCOCF3)2]2 (VII) which reacts with chelating diphosphines in the presence of NH4PF6 to give the PF6 salts of the doubly-bridged dications {[(C5Me4)2CH2][Rh2(PMe3)2(OCOCF3)2(μ-P-P)]}2+ (PP = dppm, dppe, dppb) (IX–XI). The reaction of III with [Rh(CO)2Cl]2 produces a mixture of the dinuclear complexes [(C5Me4)2CH2][Rh(CO)2]2 (XII) and [(C5Me4)2CH2][Rh2(μ-CO)2] (XIII) which are easily interconverted under mild conditions. 相似文献
19.
An equimolar mixture of Cp*Ti(CH3)3 (2) and Ph3C+[B(C6F5)4]? (1) forms a highly active and syndioselective catalyst for the polymerization of styrene, producing 96% syndiotactic polystyrene (PS) at an activity of 0.91 × 107 g PS (mol Ti)?1 (mol styrene)?1 h?1. Both activity and syndioselectivity can be increased using tri–isobutylaluminum (TIBA) to scavenge the system. ESR measurements indicate that the polymerization proceeds via titanium(IV) intermediates. Catalysts derived from 2/methylaluminoxane (MAO) as well as Cp*TiCl3/MAO also function as syndioselective styrene polymerization catalysts, but are less active than the ‘cationic’; system derived from 1 and 2. 相似文献
20.
Chao Chen Florian Eweiner Birgit Wibbeling Roland Frhlich Shunsuke Senda Yasuhiro Ohki Kazuyuki Tatsumi Stefan Grimme Gerald Kehr Gerhard Erker 《化学:亚洲杂志》2010,5(10):2199-2208
The zirconocene complex [{(C6F5)2B‐(CH2)3‐Cp}(Cp‐PtBu2)ZrCl2] ( 6 ; Cp=cyclo‐C5H4) was prepared by hydroboration of [(allyl‐Cp)(Cp‐PtBu2)ZrCl2] ( 5 ) with HB(C6F5)2 (“Piers’ borane”). It represents a frustrated Lewis pair (FLP) in which both the Lewis acid and the Lewis base were attached at the metallocene framework. Its reaction with 1‐pentyne did not result in the 1,2‐addition of or deprotonation reaction by the FLP, but rather in the 1,1‐carboboration of the triple bond, thereby obtaining a Z/E mixture (1.2:1) of the respective organometallic substituted alkenes 7 . The analogous reaction of 1‐pentyne with the phosphorous‐free system [{(C6F5)2B‐(CH2)3‐Cp)}CpZrCl2] ( 9 ) gave the respective 1,1‐carboboration products ( Z‐10 / E‐10 ≈1.3:1). 相似文献