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1.
Frédéric Justaud Dr. Frédéric Gendron Yoshiyuki Ogyu Yuki Kumamoto Prof. Dr. Akira Miyazaki Prof. Dr. Lahcène Ouahab Dr. Karine Costuas Prof. Dr. Jean‐François Halet Prof. Dr. Claude Lapinte 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(18):5742-5757
Treatment of [Cp*(dppe)Fe? C?C‐TTFMe3] ( 1 ) with Ag[PF6] (3 equiv) in DMF provides the binuclear complex [Cp*(dppe)Fe?C?C?TTFMe2?CH? CH?TTFMe2?C?C=Fe(dppe)Cp*][PF6]2 ( 2 [PF6]2) isolated as a deep‐blue powder in 69 % yield. EPR monitoring of the reaction and comparison of the experimental and calculated EPR spectra allowed the identification of the radical salt [Cp*(dppe)Fe?C?C?TTFMe2?CH][PF6]2 ([ 1‐CH ][PF6]) an intermediate of the reaction, which results from the activation of the methyl group attached in vicinal position with respect to the alkynyl–iron on the TTF ligand by the triple oxidation of 1 leading to its deprotonation by the solvent. The dimerization of [ 1‐CH ][PF6] through carbon–carbon bond formation provides 2 [PF6]2. The cyclic voltammetry (CV) experiments show that 2 [PF6]2 is subject to two sequential well‐reversible one‐electron reductions yielding the complexes 2 [PF6] and 2 . The CV also shows that further oxidation of 2 [PF6]2 generates 2 [PF6]n (n=3–6) at the electrode. Treatment of 2 [PF6]2 with KOtBu provides 2 [PF6] and 2 as stable powders. The salts 2 [PF6] and 2 [PF6]2 were characterized by XRD. The electronic structures of 2 n+ (n=0–2) were computed. The new complexes were also characterized by NMR, IR, Mössbauer, EPR, UV/Vis and NIR spectroscopies. The data show that the three complexes 2 [PF6]n are iron(II) derivatives in the ground state. In the solid state, the dication 2 2+ is diamagnetic and has a bis(allenylidene‐iron) structure with one positive charge on each iron building block. In solution, as a result of the thermal motion of the metal–carbon backbone, the triplet excited state becomes thermally accessible and equilibrium takes place between singlet and triplet states. In 2 [PF6], the charge and the spin are both symmetrically distributed on the carbon bridge and only moderately on the iron and TTFMe2 electroactive centers. 相似文献
2.
Parvin Safari Simon Gückel Dr. Josef B. G. Gluyas Prof. Stephen A. Moggach Prof. Martin Kaupp Prof. Paul J. Low 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(44):e202200926
The electronic structure and associated spectroscopic properties of ligand-bridged, bimetallic ‘mixed-valence’ complexes of the general form {M}(μ-B){M+} are dictated by the electronic couplings, and hence orbital overlaps, between the metal centers mediated by the bridge. In the case of complexes such as [{Cp*(dppe)Ru}(μ-C≡CC6H4C≡C){Ru(dppe)Cp*}]+, the low barrier to rotation of the half-sandwich metal fragments and the arylene bridge around the acetylene moieties results in population of many energy minima across the conformational energy landscape. Since orbital overlap is also sensitive to the particular mutual orientations of the metal fragment(s) and arylene bridge through a Karplus-like relationship, the different members of the population range exemplify electronic structures ranging from strongly localized (weakly coupled Robin-Day Class II) to completely delocalized (Robin-Day Class III). Here, we use electronic structure calculations with the hybrid density functional BLYP35-D3 and a continuum solvent model in combination with UV-vis-NIR and IR spectroelectrochemical studies to show that the conformational population in complexes [{Cp*(dppe)Ru}(μ-C≡CArC≡C){Ru(dppe)Cp*]+, and hence the dominant electronic structure, can be biased through the steric and electronic properties of the diethynylarylene (Ar) moiety (Ar=1,4-C6H4, 1,4-C6F4, 1,4-C6H2-2,5-Me2, 1,4-C6H2-2,5-(CF3)2, 1,4-C6H2-2,5-iPr2). 相似文献
3.
Hsueh‐Ju Liu Micah S. Ziegler T. Don Tilley 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(22):6722-6726
Reactivity studies of the thermally stable ruthenostannylene complex [Cp*(IXy)(H)2Ru Sn Trip] ( 1 ; IXy=1,3‐bis(2,6‐dimethylphenyl)imidazol‐2‐ylidene; Cp*=η5‐C5Me5; Trip=2,4,6‐iPr3C6H2) with a variety of organic substrates are described. Complex 1 reacts with benzoin and an α,β‐unsaturated ketone to undergo [1+4] cycloaddition reactions and afford [Cp*(IXy)(H)2RuSn(κ2‐O,O‐OCPhCPhO)Trip] ( 2 ) and [Cp*(IXy)(H)2RuSn(κ2‐O,C‐OCPhCHCHPh)Trip] ( 3 ), respectively. The reaction of 1 with ethyl diazoacetate resulted in a tin‐substituted ketene complex [Cp*(IXy)(H)2RuSn(OC2H5)(CHCO)Trip] ( 4 ), which is most likely a decomposition product from the putative ruthenium‐substituted stannene complex. The isolation of a ruthenium‐substituted stannene [Cp*(IXy)(H)2RuSn(Flu)Trip] ( 5 ) and stanna‐imine [Cp*(IXy)(H)2RuSn(κ2‐N,O‐NSO2C6H4Me)Trip] ( 6 ) complexes was achieved by treatment of 1 with 9‐diazofluorene and tosyl azide, respectively. 相似文献
4.
The Ruthenostannylene Complex [Cp*(IXy)H2Ru‐Sn‐Trip]: Providing Access to Unusual Ru‐Sn Bonded Stanna‐imine,Stannene, and Ketenylstannyl Complexes
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Hsueh‐Ju Liu Micah S. Ziegler Prof. Dr. T. Don Tilley 《Angewandte Chemie (International ed. in English)》2015,54(22):6622-6626
Reactivity studies of the thermally stable ruthenostannylene complex [Cp*(IXy)(H)2Ru? Sn? Trip] ( 1 ; IXy=1,3‐bis(2,6‐dimethylphenyl)imidazol‐2‐ylidene; Cp*=η5‐C5Me5; Trip=2,4,6‐iPr3C6H2) with a variety of organic substrates are described. Complex 1 reacts with benzoin and an α,β‐unsaturated ketone to undergo [1+4] cycloaddition reactions and afford [Cp*(IXy)(H)2RuSn(κ2‐O,O‐OCPhCPhO)Trip] ( 2 ) and [Cp*(IXy)(H)2RuSn(κ2‐O,C‐OCPhCHCHPh)Trip] ( 3 ), respectively. The reaction of 1 with ethyl diazoacetate resulted in a tin‐substituted ketene complex [Cp*(IXy)(H)2RuSn(OC2H5)(CHCO)Trip] ( 4 ), which is most likely a decomposition product from the putative ruthenium‐substituted stannene complex. The isolation of a ruthenium‐substituted stannene [Cp*(IXy)(H)2RuSn(?Flu)Trip] ( 5 ) and stanna‐imine [Cp*(IXy)(H)2RuSn(κ2‐N,O‐NSO2C6H4Me)Trip] ( 6 ) complexes was achieved by treatment of 1 with 9‐diazofluorene and tosyl azide, respectively. 相似文献
5.
Michael R. Hall Rachel R. Steen Dr. Marcus Korb Dr. Alexandre N. Sobolev Dr. Stephen A. Moggach Dr. Jason M. Lynam Prof. Paul J. Low 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(32):7226-7234
Reactions of [Ru{C=C(H)-1,4-C6H4C≡CH}(PPh3)2Cp]BF4 ([ 1 a ]BF4) with hydrohalic acids, HX, results in the formation of [Ru{C≡C-1,4-C6H4-C(X)=CH2}(PPh3)2Cp] [X=Cl ( 2 a-Cl ), Br ( 2 a-Br )], arising from facile Markovnikov addition of halide anions to the putative quinoidal cumulene cation [Ru(=C=C=C6H4=C=CH2)(PPh3)2Cp]+. Similarly, [M{C=C(H)-1,4-C6H4-C≡CH}(LL)Cp ]BF4 [M(LL)Cp’=Ru(PPh3)2Cp ([ 1 a ]BF4); Ru(dppe)Cp* ([ 1 b ]BF4); Fe(dppe)Cp ([ 1 c ]BF4); Fe(dppe)Cp* ([ 1 d ]BF4)] react with H+/H2O to give the acyl-functionalised phenylacetylide complexes [M{C≡C-1,4-C6H4-C(=O)CH3}(LL)Cp’] ( 3 a – d ) after workup. The Markovnikov addition of the nucleophile to the remote alkyne in the cations [ 1 a–d ]+ is difficult to rationalise from the vinylidene form of the precursor and is much more satisfactorily explained from initial isomerisation to the quinoidal cumulene complexes [M(=C=C=C6H4=C=CH2)(LL)Cp’]+ prior to attack at the more exposed, remote quaternary carbon. Thus, whilst representative acetylide complexes [Ru(C≡C-1,4-C6H4-C≡CH)(PPh3)2Cp] ( 4 a ) and [Ru(C≡C-1,4-C6H4-C≡CH)(dppe)Cp*] ( 4 b ) reacted with the relatively small electrophiles [CN]+ and [C7H7]+ at the β-carbon to give the expected vinylidene complexes, the bulky trityl ([CPh3]+) electrophile reacted with [M(C≡C-1,4-C6H4-C≡CH)(LL)Cp’] [M(LL)Cp’=Ru(PPh3)2Cp ( 4 a ); Ru(dppe)Cp* ( 4 b ); Fe(dppe)Cp ( 4 c ); Fe(dppe)Cp* ( 4 d )] at the more exposed remote end of the carbon-rich ligand to give the putative quinoidal cumulene complexes [M{C=C=C6H4=C=C(H)CPh3}(LL)Cp’]+, which were isolated as the water adducts [M{C≡C-1,4-C6H4-C(=O)CH2CPh3}(LL)Cp’] ( 6 a–d ). Evincing the scope of the formation of such extended cumulenes from ethynyl-substituted arylvinylene precursors, the rather reactive half-sandwich (5-ethynyl-2-thienyl)vinylidene complexes [M{C=C(H)-2,5-cC4H2S-C≡CH}(LL)Cp’]BF4 ([ 7 a – d ]BF4 add water readily to give [M{C≡C-2,5-cC4H2S-C(=O)CH3}(LL)Cp’] ( 8 a – d )]. 相似文献
6.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(6):1627-1631
The heterometallic complexes trans ‐[Cp(dppe)FeNCRu(o ‐bpy)CNFe(dppe)Cp][PF6]n ( 1 [PF6]n , n =2, 3, 4; o ‐bpy=1,2‐bis(2,2′‐bipyridyl‐6‐yl)ethane, dppe=1,2‐bis(diphenylphosphino)ethane, Cp=1,3‐cyclopentadiene) in three distinct states have been synthesized and fully characterized. 1 3+[PF6]3 and 1 4+[PF6]4 are the one‐ and two‐electron oxidation products of 1 2+[PF6]2, respectively. The investigated results suggest that 1 [PF6]3 is a Class II mixed valence compound. 1 [PF6]4 after a thermal treatment at 400 K shows an unusually delocalized mixed valence state of [FeIII‐NC‐RuIII‐CN‐FeII], which is induced by electron transfer from the central RuII to the terminal FeIII in 1 [PF6]4, which was confirmed by IR spectroscopy, magnetic data, and EPR and Mössbauer spectroscopy. 相似文献
7.
Influence of Central Metalloligand Geometry on Electronic Communication between Metals: Syntheses,Crystal Structures,MMCT Properties of Isomeric Cyanido‐Bridged Fe2Ru Complexes,and TDDFT Calculations
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Dr. Xiao Ma Dr. Chen‐Sheng Lin Sheng‐Min Hu Dr. Chun‐Hong Tan Dr. Yue‐Hong Wen Prof. Dr. Tian‐Lu Sheng Prof. Xin‐Tao Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(23):7025-7036
To investigate how the central metalloligand geometry influences distant or vicinal metal‐to‐metal charge‐transfer (MMCT) properties of polynuclear complexes, cis‐ and trans‐isomeric heterotrimetallic complexes, and their one‐ and two‐electron oxidation products, cis/trans‐ [Cp(dppe)FeIINCRuII(phen)2CN‐FeII(dppe)Cp][PF6]2 (cis/trans‐ 1 [PF6]2), cis/trans‐[Cp(dppe)FeIINCRuII(phen)2CNFeIII‐(dppe)Cp][PF6]3 (cis/trans‐ 1 [PF6]3) and cis/trans‐[Cp(dppe)FeIIINCRuII(phen)2CN‐FeIII(dppe)Cp][PF6]4 (cis/trans‐ 1 [PF6]4) have been synthesized and characterized. Electrochemical measurements show the presence of electronic interactions between the two external FeII atoms of the cis‐ and trans‐isomeric complexes cis/trans‐ 1 [PF6]2. The electronic properties of all these complexes were studied and compared by spectroscopic techniques and TDDFT//DFT calculations. As expected, both mixed valence complexes cis/trans‐ 1 [PF6]3 exhibited different strong absorption signals in the NIR region, which should mainly be attributed to a transition from an MO that is delocalized over the RuII‐CN‐FeII subunit to a FeIII d orbital with some contributions from the co‐ligands. Moreover, the NIR transition energy in trans‐ 1 [PF6]3 is lower than that in cis‐ 1 [PF6]3, which is related to the symmetry of their molecular orbitals on the basis of the molecular orbital analysis. Also, the electronic spectra of the two‐electron oxidized complexes show that trans‐ 1 [PF6]4 possesses lower vicinal RuII→FeIII MMCT transition energy than cis‐ 1 [PF6]4. Moreover, the assignment of MMCT transition of the oxidized products and the differences of the electronic properties between the cis and trans complexes can be well rationalized using TDDFT//DFT calculations. 相似文献
8.
[{Cp*(CO)2Fe}6Sn6O8]2+, a Cationic Tin Oxo Cluster with Organometallic Substituents The reaction of [{Cp*(CO)2Fe}SnCl3] 1 (Cp* = Pentamethylcyclopentadienyl) with Ag2O in acetone leads to the formation of [{Cp*(CO)2Fe}6Sn6O8][AgCl2]2( 2 ). 2 contains the novel tin oxo cluster cation [{Cp*(CO)2Fe}6Sn6O8]2+ which consists of six {Cp*(CO)2Fe}Sn‐groups bridged by eight μ3 oxygen atoms (Sn—O = 209.2(3)‐212.5(3) pm). The resulting Sn6O8 cage exhibits a distorted rhombodocahedral structure. The [AgCl2]— anion is essentially linear with a Ag—Cl bond length of 250.3(3) pm. 相似文献
9.
Reactions of the cyanide complexes of the type [(Ind)Ru(PPh3)2CN] (1), [(Ind)Ru(dppe)CN] (2), [(Cp)Ru(PPh3)2CN] (3), with the corresponding chloro complexes [(Ind)Ru(PPh3)2Cl] (4), [(Ind)Ru(dppe)Cl] (5), [(Cp)Ru(PPh3)2Cl] (6), in the presence of NH4PF6 salt give homometallic cyano-bridged compounds of the type [(Ind)(PPh3)2Ru-CN-Ru(PPh3)2(Cp)]PF6 (7), [(Ind)(PPh3)2Ru-CN-Ru(PPh3)2(Ind)] PF6 where Ind = indenyl, η5-C9H7, (8), [(Cp)(PPh3)2Ru-CN-Ru(dppe)(Ind)]PF6, dppe = (Ph2PCH2CH2PPh2) (9), [(Ind(dppe)Ru-CN-Ru(PPh3)2(Ind)PF6 (10) and [(Ind)(dppe)Ru-CN-Ru(PPh3)2(Cp)]PF6 (11) respectively. Reaction of complex3 with [(p-cymene)RuCl2]2 dimer gave a mixed dimeric complex [(Cp)Ru(PPh3)2-CN-RuCl2(p-cymene)] (12). All these complexes have been characterized by IR,1H,13C and31P NMR spectroscopy and C, H, N analyses. 相似文献
10.
Dr. Qing-Dou Xu Dr. Xiao Ma Chen Zeng Dr. Shao-Dong Su Sheng-Min Hu Ying-Ying Huang Prof. Xin-Tao Wu Prof. Tian-Lu Sheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(34):e202104486
To investigate the effects of cis/trans-configuration of the cyanidometal bridge and the electron donating ability of the auxiliary ligand on the cyanidometal bridge on metal to metal charge transfer (MMCT) in cyanidometal-bridged mixed valence compounds, two groups of trinuclear cyanidometal-bridged compounds cis/trans-[Cp(dppe)Fe(μ-NC)Ru(4,4’-dmbpy)2(μ-CN)Fe(dppe)Cp][PF6]n (n=2 ( cis/trans - 1[PF6]2 ), 3 ( cis/trans - 1[PF6]3 ), 4 ( cis/trans - 1[PF6]4 )) and cis/trans-[Cp(dppe)Fe(μ-NC)Ru(bpy)2(μ-CN)Fe(dppe)Cp][PF6]3 ( cis/trans - 2[PF6]3 ) were synthesized and fully characterized. The experimental results indicate that for these one- and two-electron oxidation mixed valence compounds, the trans-configuration compounds are more beneficial for MMCT than the cis-configuration compounds, and increasing the electron donating ability of the auxiliary ligand on the cyanidometal bridge is also conductive to MMCT. Moreover, compounds cis/trans - 1[PF6]n (n=3, 4) and cis/trans - 2[PF6]3 belong to localized compounds by analyzing the experimental characterization results, supported by the TDDFT calculations. 相似文献
11.
《Journal of Coordination Chemistry》2012,65(8):1367-1379
The coordination chemistry of cross-conjugated ligands and the effect of cross-conjugation on the nature of metal–metal and metal–ligand interactions have received limited attention. To explore the effects of cross-conjugation eight ruthenium complexes were synthesized, mononuclear complexes of two isomeric cross-conjugated [3]radialenes [RuCp(PPh3)2(L)]PF6 and [{RuCp*(dppe)}(L)]PF6 (L?=?hexakis(4-cyanophenyl)[3]radialene, 2; hexakis(3-cyanophenyl)[3]radialene, 3), and dinuclear complexes [{RuCp(PPh3)2}2(L)](PF6)2 and [{RuCp*(dppe)}2(L)](PF6)2 of the diarylmethane precursors (L?=?4,4′-dicyanodiphenylmethane, 4; 3,3′-dicyanodiphenylmethane, 5) to the [3]radialenes. Considerable synthetic challenges allowed only clean isolation of mononuclear complexes of the multidentate radialenes 2 and 3. As expected, coordinating a positively charged metal induces a red shift for the π–π* transition in complexes of ligand 2, but unexpectedly a blue shift for the same transition in complexes of 3 was observed. This points to conformational differences for the [3]radialene in the ruthenium complexes of the para- (2) versus meta- (3) substituted hexaaryl[3]radialenes. Cyclic voltammetry indicates that the methylene spacer in 4 and 5 does not enable any interaction between metal centers and the absorption behavior is essentially as observed for [Ru(NCPh)(PPh3)2Cp]PF6 and [Ru(NCPh)(dppe)Cp*]PF6 but generally with a slight red shift in absorbance maxima. 相似文献
12.
Alexander Filippou Peter Portius Athanassios Philippopoulos Gabriele Kociok‐Khn Burkhard Ziemer 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(9):e378-e379
trans‐[MoCl2(dppe)2] [dppe is 1,2‐ethanediylbis(diphenylphosphine), C26H24P2] was obtained as a side product from the reaction of trans‐[Mo(dppe)2(N2)2] with Cp*GeCl to give the germylyne complex trans‐[Cl(dppe)2Mo[triple‐bond]Ge(η1‐Cp*)]. The crystal structures of the hemipentane (0.5C5H12) and ditetrahydrofuran (2C4H8O) solvates of trans‐[MoCl2(dppe)2], (IIIa) and (IIIb), respectively, have been determined. 相似文献
13.
Dr. Martin Fleischmann Dr. Fabian Dielmann Dr. Gábor Balázs Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(43):15248-15251
The oxidation of the 28 VE cyclo‐E6 triple‐decker complexes [(CpRMo)2(μ,η6:η6‐E6)] (E=P, CpR=Cp( 2 a ), Cp*( 2 b ), CpBn( 2 c )=C5(CH2Ph)5; E=As, CpR=Cp*( 3 )) by Cu+ or Ag+ leads to cationic 27 VE complexes that retain their general triple‐decker geometry in the solid state. The obtained products have been characterized by cyclic voltammetry (CV), EPR, Evans NMR, multinuclear NMR spectroscopy, MS, and structural analysis by single‐crystal X‐ray diffraction. The cyclo‐E6 middle decks of the oxidized complexes are distorted to a quinoid ( 2 a ) or bisallylic ( 2 b , 2 c , 3 ) geometry. DFT calculations of 2 a , 2 b , and 3 persistently result in the bisallylic distortion as the minimum geometry and show that the oxidation leads to a depopulation of the σ‐system of the cyclo‐E6 ligands in 2 a – 3 . Among the starting complexes, 2 c is reported for the first time including its preparation and full characterization. 相似文献
14.
The reaction of the neutral carborane C2B9H13 with Cp*M(CH3)3 (M = Zr (a), Hf (b); Cp* = η5-C5Me5) yields [Cp(C2B9H11)M(CH3)]n (3a, b). Complexes 3a, b form THF adducts Cp*(C2B9H11)M(CH3)(THF) 4, insert 2-butyne to yield Cp*(C2B9H11)M{C(Me=CMe2} 5, and undergo methane elimination upon thermolysis to yield methylene-bridged complexes [Cp*(C2B9H11)M]2(μ-CH2) (6). These chemical studies, and companion structural and theoretical studies establish that 3a, b are neutral analogues of the cationic Cp2M(R)+ species (1; Cp = η5-C5H5) and Cp2M(R)(L)+ (2) which are believed to be active in Cp2MX2-based Ziegler catalysts. Despite the lower metal charge, 3–6 exhibit characteristic “electrophilic metal alkyl” properties including agostic M-H-C and M-H-B interactions, high insertion and intramolecular C-H activation reactivity, and high ethylene polymerization and propene oligomerization activity. These observations suggest that the key requirement for high insertion/polymerization activity in metallocene systems is high metal unsaturation (i.e. two empty metal-centered orbitals) rather than charge. 相似文献
15.
Prof. Dr. Takako Muraoka Ryosuke Ishizeki Shun Tanabe Dr. Keiji Ueno 《欧洲无机化学杂志》2023,26(18):e202300124
Silanethione compounds, R2Si=S, have been recognized as highly reactive species. One reliable way to stabilize silanethione is its coordination to transition metal fragments to convert silanethione-coordinated transition metal complexes. Herein, we report the synthesis, structure, and reactivity of a second cationic silanethione tungsten complex [Cp*(OC)3W{S=SiR2(py)}]TFPB (R=Me ( 5 a ), Ph ( 5 b ), Cp*: η5-C5Me5, py: pyridine, and TFPB−: [B{3,5-(CF3)2C6H3}4]−). Complex 5 was obtained by H− abstraction from the Si atom in the corresponding silylsulfanyl complex Cp*(OC)3W(SSiR2H) ( 4 ) with Ph3CTFPB, followed by the addition of pyridine. The reaction of 5 with PhNCS and PMe3 produced [Cp*(OC)3W{SSiR2N(Ph)C(PMe3)2}]TFPB (R=Me ( 6 a ), Ph ( 6 b )) via the elimination of pyridine and the addition of the 1,3-dipolar species PhNC(PMe3)2 ( A ) to the Si atom. 相似文献
16.
H ? C Bond Cleavage in Ferrocene by Organylruthenium Complexes Cp*(Me3P)2RuCH2CMe3 ( 1 ) reacts at 85°C with ferrocene ( 2 ) by cleavage of one H? C bond in 2 to give CpFe[η5-C5H4Ru(PMe3)2Cp*] ( 3 ) (Cp = η5-C5H5; Cp* = η5-C5Me5) and neopentane. The ruthenium atom in 3 has a distorted tetrahedral geometry, the planar Cp ligands in the ferrocenyl fragment are eclipsed. Solutions of 3 in [D6]benzene or [D8]THF exhibit H? D exchange of the ferrocenyl protons. In the [D8]THF molecule only the α-deuterium atoms are exchanged. Reaction pathways for this exchange are discussed. 相似文献
17.
Takashi Tsuno Yu Sugiyama Henri Brunner Michael Bodensteiner Kosei Lee 《Journal of Coordination Chemistry》2017,70(20):3459-3470
Treatment of NiCl2 with the tripod ligand (LMent,SC)-1H led to (LMent,SC)-[Cp(PNMent)NiCl] in which the potentially tridentate ligand coordinated to the metal center in a bidentate way via the cyclopentadienyl system and the phosphorus atom. In the presence of NH4PF6 [(LMent,SC)-[Cp(PNMent)NiCl] readily underwent Cl/PPh3 exchange to give (LMent,SC)-[Cp(PNMent)NiPPh3]PF6. Reaction of (LMent,SC)-[Cp(PNMent)NiCl] with 0.5 eq. of dppe afforded [{(LMent,SC)-[Cp(PNMent)Ni]}2dppe](PF6)2. (LMent,SC)-[Cp(PNMent)NiPPh3]PF6 and [{(LMent,SC)-[Cp(PNMent)Ni]}2dppe](PF6)2 were characterized by NMR and MS spectroscopy, and also by single crystal X-ray diffraction. The cyclopentadienyl ligand of (LMent,SC)-[Cp(PNMent)NiPPh3]PF6 shows a distortion intermediate between the ene-allyl and diene types, while the two cyclopentadienyl ligands of [{(LMent,SC)-[Cp(PNMent)Ni]}2dppe](PF6)2 have intermediate and diene distortions, respectively. According to the temperature dependent NMR spectra of (LMent,SC)-[Cp(PNMent)NiPPh3]PF6 and [{(LMent,SC)-[Cp(PNMent)Ni]}2dppe](PF6)2 two different conformations of the tether in the Cp(PNMent)Ni system could be frozen out at low temperatures. 相似文献
18.
On the Reactivity of the Ferriophosphaalkene (Z)‐[Cp*(CO)2Fe‐P=C(tBu)NMe2] towards Propiolates HC≡C‐CO2R (R=Me, Et) and Acetylene Dicarboxylates RO 2C‐C≡C‐CO2R (R=Me, Et, tBu) The reaction of equimolar amounts of (Z)‐[Cp*(CO)2Fe‐P=C(tBu)NMe2] 3 and methyl‐ and ethyl‐propiolate ( 2a, b ) or of 3 and dialkyl acetylene dicarboxylates 1a (R=Me), 1b (Et), 1c (tBu) afforded the five‐membered metallaheterocycles [Cp*(CO) =C(tBu)NMe2] ( 4a, b ) and [Cp*(CO) =C(tBu)NMe2] ( 5a—c ). The molecular structures of 4b and 5a were elucidated by single crystal X‐ray analyses. Moreover, the reactivity of 4b towards ethereal HBF4 was investigated. 相似文献
19.
Jiliang Zhou Liu Leo Liu Levy L. Cao Douglas W. Stephan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(16):5461-5466
Double chloride abstraction of Cp*AsCl2 gives the dicationic arsenic species [(η5‐Cp*)As(tol)][B(C6F5)4]2 ( 2 ) (tol=toluene). This species is shown to exhibit Lewis super acidity by the Gutmann–Beckett test and by fluoride abstraction from [NBu4][SbF6]. Species 2 participates in the FLP activation of THF affording [(η2‐Cp*)AsO(CH2)4(THF)][B(C6F5)4]2 ( 5 ). The reaction of 2 with PMe3 or dppe generates [(Me3P)2As][B(C6F5)4] ( 6 ) and [(σ‐Cp*)PMe3][B(C6F5)4] ( 7 ), or [(dppe)As][B(C6F5)4] ( 8 ) and [(dppe)(σ‐Cp*)2][B(C6F5)4]2 ( 9 ), respectively, through a facile cleavage of C?As bonds, thus showcasing unusual reactivity of this unique As‐containing compound. 相似文献
20.
[{Cp*(OC)2Re}2(μ‐POH)], a Dinuclear Complex with a Bridging Hydroxiphosphinidene Ligand The reaction of [{Cp*(OC)2Re}4(μ4‐η1 : η1 : η1 : η1‐P2)] ( 1 ) with 0.1 m HCl gives [{Cp*(OC)2Re}2(μ‐POH)] ( 2 ), the X‐ray crystal structure of which reveals a dinuclear rhenium complex with a μ‐POH (hydroxiphosphinidene) ligand. 相似文献