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1.
Heterobimetallic Phosphanido-bridged Dinuclear Complexes - Syntheses of cis-rac-[(η-C5H4R)2Zr{μ-PH(2,4,6-iPr3C6H2)}2M(CO)4] (R?Me, M?Cr, Mo; R?H, M?Mo) The zirconocene bisphosphanido complexes [(η-C5H4R)2Zr{PH(2,4,6-iPr3C6H2)}2] (R?Me, H) react with [(NBD)M(CO)4] (NBD?norbornadiene, M?Cr, Mo) to give only one diastereomer of the phosphanido-bridged heterobimetallic dinuclear complexes cis-rac-[(η-C5H4R)2Zr{μ-PH(2,4,6-iPr3C6H2)}2M(CO)4] [R?Me, M?Cr ( 1 ), Mo ( 2 ); R?H, M?Mo ( 3 )]. However, no reaction was observed between [(η-C5H5)2Zr{PH(2,4,6-tBu3 C6H2)}2] and [Pt(PPh3)4]. 1—3 were characterised spectroscopically. For 1—3 , the presence of the racemic isomer was shown by NMR spectroscopy. No reaction was observed at room temperature for 3 and CS2, (NO)BF4, Me3NO or PH(2,4,6-Me3C6H2)2. With Et2AlH or PhC?CH decomposition of 3 was observed. 相似文献
2.
Four‐Membered Heterometallacyclic d0 and d1 Complexes of Group 4 Metallocenes with Amidato Ligands 下载免费PDF全文
Dr. Martin Haehnel Jacqueline B. Priebe Jacky C.‐H. Yim Dr. Anke Spannenberg Prof. Dr. Angelika Brückner Prof. Dr. Laurel L. Schafer Prof. Dr. Uwe Rosenthal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(25):7752-7758
A study of the coordination chemistry of different amidato ligands [(R)N?C(Ph)O] (R=Ph, 2,6‐diisopropylphenyl (Dipp)) at Group 4 metallocenes is presented. The heterometallacyclic complexes [Cp2M(Cl){κ2‐N,O‐(R)N?C(Ph)O}] M=Zr, R=Dipp ( 1 a ), Ph ( 1 b ); M=Hf, R=Ph ( 2 )) were synthesized by reaction of [Cp2MCl2] with the corresponding deprotonated amides. Complex 1 a was also prepared by direct deprotonation of the amide with Schwartz reagent [Cp2Zr(H)Cl]. Salt metathesis reaction of [Cp2Zr(H)Cl] with deprotonated amide [(Dipp)N?C(Ph)O] gave the zirconocene hydrido complex [Cp2M(H){κ2‐N,O‐(Dipp)N?C(Ph)O}] ( 3 ). Reaction of 1 a with Mg did not result in the desired Zr(III) complex but in formation of Mg complex [(py)3Mg(Cl) {κ2‐N,O‐(Dipp)N?C(Ph)O}] ( 4 ; py=pyridine). The paramagnetic complexes [Cp′2Ti{κ2‐N,O‐(R)N?C(Ph)O}] (Cp′=Cp, R=Ph ( 7 a ); Cp′=Cp, R=Dipp ( 7 b ); Cp′=Cp*, R=Ph ( 8 )) were prepared by the reaction of the known titanocene alkyne complexes [Cp2′Ti(η2‐Me3SiC2SiMe3)] (Cp′=Cp ( 5 ), Cp′=Cp* ( 6 )) with the corresponding amides. Complexes 1 a , 2 , 3 , 4 , 7 a , 7 b , and 8 were characterized by X‐ray crystallography. The structure and bonding of complexes 7 a and 8 were also characterized by EPR spectroscopy. 相似文献
3.
Reactions of 2‐Substituted Pyridines with Titanocenes and Zirconocenes: Coupling versus Dearomatisation 下载免费PDF全文
Dr. Fabian Reiß Dr. Kai Altenburger Dr. Lisanne Becker Kathleen Schubert Dr. Haijun Jiao Dr. Anke Spannenberg Dr. Dirk Hollmann Dr. Perdita Arndt Prof. Dr. Uwe Rosenthal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(10):3361-3369
Reactions of group 4 metallocene sources with 2‐substituted pyridines were investigated to evaluate their coordination type between innocent and reductive dearomatisation as well as to probe the possibility for couplings. A dependence on the cyclopentadienyl ligands (Cp, Cp*), the metals (Ti, Zr), and the substrates (2‐phenyl‐, 2‐acetyl‐, and 2‐iminopyridine) was observed. While 2‐phenylpyridine is barely reactive, 2‐acetylpyridine reacts vigorously with the Cp‐substituted complexes and selectively with their Cp* analogues. With 2‐iminopyridine, in all cases selective reactions were observed. In the isolated [Cp2Ti], [Cp2Zr], and [Cp*2Zr] compounds the substrate coordinates by its pyridyl ring and the unsaturated side‐chain. Subsequently, the pyridine was dearomatised, which is most pronounced in the [Cp*2Zr] compounds. Using [Cp*2Ti] leads to the unexpected paramagnetic complexes [Cp*2TiIII(N,O‐acpy)] and [Cp*2TiIII(N,N′‐impy)]. This highlights the non‐innocent character of the pyridyl substrates. 相似文献
4.
Lisanne Becker Dr. Vladimir V. Burlakov Dr. Perdita Arndt Dr. Anke Spannenberg Dr. Wolfgang Baumann Dr. Haijun Jiao Prof. Dr. Uwe Rosenthal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(13):4230-4237
Reactions of Group 4 metallocene alkyne complexes [Cp′2M(η2‐Me3SiC2SiMe3)] ( 1 : M=Zr, Cp′=Cp*=η5‐pentamethylcyclopentadienyl; 2 a : M=Ti, Cp′=Cp*, and 2 b : M=Ti, Cp′2=rac‐(ebthi)=rac‐1,2‐ethylene‐1,1′‐bis(η5‐tetrahydroindenyl)) with diphenylacetonitrile (Ph2CHCN) and of the seven‐membered zirconacyclocumulene 3 with phenylacetonitrile (PhCH2CN) were investigated. Different compounds were obtained depending on the metal, the cyclopentadienyl ligand and the reaction temperature. In the first step, Ph2CHCN coordinated to 1 to form [Cp*2Zr(η2‐Me3SiC2SiMe3)(NCCHPh2)] ( 4 ). Higher temperatures led to elimination of the alkyne, coordination of a second Ph2CHCN and transformation of the nitriles to a keteniminate and an imine ligand in [Cp*2Zr(NC2Ph2)(NCHCHPh2)] ( 5 ). The conversion of 4 to 5 was monitored by using 1H NMR spectroscopy. The analogue titanocene complex 2 a eliminated the alkyne first, which led directly to [Cp*2Ti(NC2Ph2)2] ( 6 ) with two keteniminate ligands. In contrast, the reaction of 2 b with diphenylacetonitrile involved a formal coupling of the nitriles to obtain the unusual four‐membered titanacycle 7 . An unexpected six‐membered fused zirconaheterocycle ( 8 ) resulted from the reaction of 3 with PhCH2CN. The molecular structures of complexes 4 , 5 , 6 , 7 and 8 were determined by X‐ray crystallography. 相似文献
5.
Dr. Katharina Kaleta Frank Strehler Dr. Alexander Hildebrandt Dr. Torsten Beweries Dr. Perdita Arndt Dr. Tobias Rüffer Dr. Anke Spannenberg Prof. Dr. Heinrich Lang Prof. Dr. Uwe Rosenthal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(40):12672-12680
The reaction of different metallocene fragments [Cp2M] (Cp=η5‐cyclopentadienyl, M=Ti, Zr) with diferrocenylacetylene and 1,4‐diferrocenylbuta‐1,3‐diyne is described. The titanocene complexes form the highly strained three‐ and five‐membered ring systems [Cp2Ti(η2‐FcC2Fc)] ( 1 ) and [Cp2Ti(η4‐FcC4Fc)] ( 2 ) (Fc=[Fe(η5‐C5H4)(η5‐C5H5)]) by addition of the appropriate alkyne or diyne to Cp2Ti. Zirconocene precursors react with diferrocenyl‐ and ferrocenylphenylacetylene under C? C bond coupling to yield the metallacyclopentadienes [Cp2Zr(C4Fc4)] ( 3 ) and [Cp2Zr(C4Fc2Ph2)] ( 5 ), respectively. The exchange of the zirconocene unit in 3 by hydrogen atoms opens the route to the super‐crowded ferrocenyl‐substituted compound tetraferrocenylbutadiene ( 4 ). On the other hand, the reaction of 1,4‐diferrocenylbuta‐1,3‐diyne with zirconocene complexes afforded a cleavage of the central C? C bond, and thus, dinuclear [{Cp2Zr(μ‐η1:η2‐C?CFc)}2] ( 6 ) that consists of two zirconocene acetylide groups was formed. Most of the complexes were characterized by single‐crystal X‐ray crystallography, showing attractive multinuclear molecules. The redox properties of 3 , 5 , and 6 were studied by cyclic voltammetry. Upon oxidation to 3 n+, 5 n+, and 6 n+ (n=1–3), decomposition occured with in situ formation of new species. The follow‐up products from 3 and 5 possess two or four reversible redox events pointing to butadiene‐based molecules. However, the dinuclear complex 6 afforded ethynylferrocene under the measurement conditions. 相似文献
6.
Prof. Uwe Rosenthal 《ChemistryOpen》2021,10(12):1234-1243
Recently published reactions of group 4 metallocene bis(trimethylsilyl)acetylene (btmsa) complexes from the last two years are reviewed. Complexes like Cp’2Ti(η2-Me3SiC2SiMe3) and Cp2Zr(py)(η2-Me3SiC2SiMe3) with Cp’ as Cp (cyclopentadienyl) and Cp* (pentamethylcyclopentadienyl) have been considered (py=pyridine). These complexes can liberate a reactive low-valent titanium or zirconium center by dissociation of the ligands and act as ‘‘masked’’ MII complexes (M=Ti, Zr). They represent excellent sources for the clean generation of the reactive coordinatively and electronically unsaturated complex fragments [Cp’2M]. This is the reason why they were used for many synthetic and catalytic reactions during the last years. As an update to several review articles on this topic, this contribution provides an update with recent examples of preparative organometallic and organic chemistry of these complexes, acting as reagents for a wide range of coordinating and coupling reactions. In addition, applications and investigations concerning reaction products derived from this chemistry are mentioned, too. 相似文献
7.
D. Thomas N. Peulecke V. V. Burlakov B. Heller W. Baumann A. Spannenberg R. Kempe U. Rosenthal R. Beckhaus 《无机化学与普通化学杂志》1998,624(5):919-924
Desactivation of Catalysts in the Polymerization of Acetylene by Bis(trimethylsilyl)acetylene Complexes of Titanocene or Zirconocene Unexpected inactive byproducts were observed in the catalytic polymerization of acetylene using metallocene alkyne complexes Cp2M(L)(η2-Me3SiC2SiMe3), 1 : M = Ti, without L; 2 : M = Zr, L = thf. The reaction of 1 was investigated in detail by NMR to give quantitatively at –20 °C the titanacyclopentadiene Cp2Ti–CH=CH–C(SiMe3)=C(SiMe3) ( 3 ). Around 0 °C 3 starts to rearrange to yield the dihydroindenyl complex 4 via coupling of one Cp-ligand with the titanacyclopentadiene. In the reaction of 2 under analogous conditions a zirconacyclopentadiene Cp2Zr–CH=CH–C(SiMe3)=C(SiMe3) ( 5 ) and the dimeric complex [Cp2Zr(C(SiMe3)=CH(SiMe3)]2[μ-σ(1,2)-C≡C] ( 6 ) were observed. Whereas 5 decomposes to a mixture of unidentified paramagnetic species, 6 was isolated and investigated by NMR spectroscopy and X-ray analysis. In the reaction of rac-(ebthi)Zr(η2-Me3SiC2SiMe3) (ebthi = ethylenbistetrahydroindenyl) with 2-ethynyl-pyridine the complex rac-(ebthi)ZrC(SiMe3)=CH(SiMe3)](σ-C≡CPy) 7 was obtained, which was investigated by an X-ray analysis. 相似文献
8.
Veronika Heinl Dr. Monika Schmidt Dr. Maria Eckhardt Dr. Miriam Eberl Dr. Andreas E. Seitz Dr. Gábor Balázs Dr. Michael Seidl Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(45):11649-11655
The use of [Cp′′2Zr(η1:1-E4)] (E=P ( 1 a ), As ( 1 b ), Cp′′=1,3-di-tert-butyl-cyclopentadienyl) as phosphorus or arsenic source, respectively, gives access to novel stable polypnictogen transition metal complexes at ambient temperatures. The reaction of 1 a/1 b with [CpRNiBr]2 (CpR=CpBn (1,2,3,4,5-pentabenzyl-cyclopentadienyl), Cp′′′ (1,2,4-tri-tert-butyl-cyclopentadienyl)) was studied, to yield novel complexes depending on steric effects and stoichiometric ratios. Besides the transfer of the complete En unit, a degradation as well as aggregation can be observed. Thus, the prismane derivatives [(Cp′′′Ni)2(μ,η3:3-E4)] ( 2 a (E=P); 2 b (E=As)) or the arsenic containing cubane [(Cp′′′Ni)3(μ3-As)(As4)] ( 5 ) are formed. Furthermore, the bromine bridged cubanes of the type [(CpRNi)3{Ni(μ-Br)}(μ3-E)4]2 (CpR=Cp′′′: 6 a (E=P), 6 b (E=As), CpR=CpBn: 8 a (E=P), 8 b (E=As)) can be isolated. Here, a stepwise transfer of En units is possible, with a cyclo-E42− ligand being introduced and unprecedented triple-decker compounds of the type [{(CpRNi)3Ni(μ3-E)4}2(μ,η4:4-E′4)] (CpR=CpBn, Cp′′′; E/E′=P, As) are obtained. 相似文献
9.
V. V. Burlakov V. S. Bogdanov K. A. Lyssenko A. Spannenberg P. V. Petrovskii W. Baumann P. Arndt M. Kh. Minacheva B. N. Strunin U. Rosenthal V. B. Shur 《Russian Chemical Bulletin》2012,61(1):165-173
The interaction of the Negishi reagent Cp2ZrBun 2 with 1,4-bis(tert-butyl)butadiyne ButC≡C-C≡CBut leads to four products: a five-membered zirconacyclocumulene complex Cp2Zr(η4-ButC4But) (2) synthesized earlier by another method, the previously unknown seven-membered zirconacyclocumulene Cp2Zr[η4-ButC4(But)-C(C2But)=CBut] (3) as well as small amounts of the zirconocene binuclear butatrienyl complex Cp2(Bun)Zr(ButC4But)Zr(Bun)Cp2 (4), and the dimeric acetylide [Cp2ZrC≡CBut]2 (5). The structure of complexes 2–5 was established by X-ray diffraction studies. 相似文献
10.
A. I. Sizov T. M. Zvukova V. K. Bel'sky B. M. Bulychev 《Russian Chemical Bulletin》1998,47(6):1186-1192
The reactions of Cp2TiH2AlH2·Et2O (1) with HN(C2H4)2O, HOC2H4OMe, and water afforded the complexes {Cp2TiH2AlH[μ-N(C2H4)2O]}2 (5), [Cp2TiH2AlH(μ-OC2H4OMe)]2 (6) and (Cp2TiH2AlH)2O (4), respectively. Compounds 5 and 6 are dimers containing bridging Al?E2?Al fragments (E=N or O). Complex 6 in solution converted to the hexanuclear compound [(η5?Cp)2Ti(μ?H(2AlH]2(μ?OC2H4OMe)[(μ1:μ5?C5H4)Ti(μ5?Cp)(μ?H)]2 (8). The structures of complexes 5 and 8 were established by X-ray diffraction analysis. The rates of hydrogenation of hex-1-ene were determined using compounds 4–6 and the complexes [Cp2TiH2AlH(NEt2)]2 and [Cp2TiH2AlH(OEt)]2 as catalysts. The probable mechanism of hydrogenation with the participation of bimetallic hydride complexes of aluminum and titanocene is discussed. 相似文献
11.
Dr. Cédric Boulho Dr. Harmen S. Zijlstra Alexander Hofmann Prof. Dr. Peter H. M. Budzelaar Prof. Dr. Sjoerd Harder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(48):17450-17459
Reaction of (TBBP)AlMe ? THF with [Cp*2Zr(Me)OH] gave [(TBBP)Al(THF)?O?Zr(Me)Cp*2] (TBBP=3,3’,5,5’‐tetra‐tBu‐2,2'‐biphenolato). Reaction of [DIPPnacnacAl(Me)?O?Zr(Me)Cp2] with [PhMe2NH]+[B(C6F5)4]? gave a cationic Al/Zr complex that could be structurally characterized as its THF adduct [(DIPPnacnac)Al(Me)?O?Zr(THF)Cp2]+[B(C6F5)4]? (DIPPnacnac=HC[(Me)C=N(2,6‐iPr2?C6H3)]2). The first complex polymerizes ethene in the presence of an alkylaluminum scavenger but in the absence of methylalumoxane (MAO). The adduct cation is inactive under these conditions. Theoretical calculations show very high energy barriers (ΔG=40–47 kcal mol?1) for ethene insertion with a bridged AlOZr catalyst. This is due to an unfavorable six‐membered‐ring transition state, in which the methyl group bridges the metal and ethene with an obtuse metal‐Me‐C angle that prevents synchronized bond‐breaking and making. A more‐likely pathway is dissociation of the Al‐O‐Zr complex into an aluminate and the active polymerization catalyst [Cp*2ZrMe]+. 相似文献
12.
(Phosphinoamide)(cyclopentadienyl)titanium(IV) complexes of the type Cp*TiCl2(η2-Ph2PNR) [Cp*=C5Me5; R = t-Bu (2a), R = n-Bu (2b), R = Ph (2c)] have been prepared by the reaction of Cp*TiCl3 with the corresponding lithium phosphinoamides. The structure of Cp*TiCl2(η2-Ph2PNtBu) (2a) and Cp*TiCl2(η2-Ph2PNPh) (2c) have been determined by X-ray crystallography. These complexes exhibited moderate catalytic activities for ethylene polymerization in the presence of modified methylaluminoxane (MMAO). Catalytic activity of up to 2.5 × 106 g/(mol Ti h) was observed when activated by i-Bu3Al/Ph3CB(C6F5)4. 相似文献
13.
Heterometallic Complexes with E6 Ligands (E = P, As) The reaction of [Cp*Co(μ-CO)]2 1 with the sandwich complexes [Cp*Fe(η5-E5)] 2 a: E = P, 2 b: E = As in decalin at 190°C affords besides [CpCo2E4] 4: E = P, 7: E = As and [CpFe2P4] 5 the trinuclear complexes [(Cp*Fe)2(Cp*Co)(μ-η2-P2)(μ3-η1:2:1-P2)2] 3 as well as [(Cp*Fe)2(Cp*Co)(μ3-η2:2:2-As3)2] 6 . With [Mo(CO)5(thf)] 3 and 6 form in a build-up reaction the tetranuclear clusters [(Cp*Fe)2(Cp*Co)E6{Mo(CO)3}] 10: E = P, 11: E = As. 3, 6 and 11 have been further characterized by an X-ray crystal structure determination. 相似文献
14.
Reactions of Group 4 Metallocenes with Monosubstituted Acetonitriles: Keteniminate Formation versus CC Coupling 下载免费PDF全文
Lisanne Becker Dr. Martin Haehnel Dr. Anke Spannenberg Dr. Perdita Arndt Dr. Uwe Rosenthal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(8):3242-3248
The reactions of the Group 4 metallocene dichlorides [Cp′2MCl2] ( 1 a : M=Ti, Cp′=Cp*=η5‐pentamethylcyclopentadienyl, 1 b : M=Zr, Cp′=Cp=η5‐cyclopentadienyl) with lithiated MesCH2?C?N gave [Cp*2TiCl(N=C=C(HMes))] ( 3 ; Mes=mesityl) in the case of 1 a . For compound 1 b , a nitrile–nitrile coupling resulted in a five‐membered bridge in 4 . The reaction of the metallocene alkyne complex [Cp*2Zr(η2‐Me3SiC2SiMe3)] ( 2 ) with PhCH2?C?N led in the first step to the unstable product [Cp*2Zr(η2‐Me3SiC2SiMe3)(NC?CH2Ph)] ( 5 ). After the elimination of the alkyne, a mixture of products was formed. By variation of the solvent and the reaction temperature, three compounds were isolated: a diazadiene complex 6 , a bis(keteniminate) complex 7 , and 8 with a keteniminate ligand and a five‐membered metallacycle. Subsequent variation of the Cp ligand and the metal center by using [Cp2Zr] and [Cp*2Ti] with Me3SiC2SiMe3 in the reactions with PhCH2?C?N gave complex mixtures. 相似文献
15.
Highly Strained Heterometallacycles of Group 4 Metallocenes with Bis(diphenylphosphino)amide Ligands
Martin Haehnel Sven Hansen Dr. Anke Spannenberg Dr. Perdita Arndt Dr. Torsten Beweries Prof. Dr. Uwe Rosenthal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(34):10546-10553
A study regarding coordination chemistry of the bis(diphenylphosphino)amide ligand Ph2P‐N‐PPh2 at Group 4 metallocenes is presented herein. Coordination of N,N‐bis(diphenylphosphino)amine ( 1 ) to [(Cp2TiCl)2] (Cp=η5‐cyclopentadienyl) generated [Cp2Ti(Cl)P(Ph2)N(H)PPh2] ( 2 ). The heterometallacyclic complex [Cp2Ti(κ2‐P,P‐Ph2P‐N‐PPh2)] ( 3 Ti ) can be prepared by reaction of 2 with n‐butyllithium as well as from the reaction of the known titanocene–alkyne complex [Cp2Ti(η2‐Me3SiC2SiMe3)] with the amine 1 . Reactions of the lithium amide [(thf)3Li{N(PPh2)2}] with [Cp2MCl2] (M=Zr, Hf) yielded the corresponding zirconocene and hafnocene complexes [Cp2M(Cl){κ2‐N,P‐N(PPh2)2}] ( 4 Zr and 4 Hf ). Reduction of 4 Zr with magnesium gave the highly strained heterometallacycle [Cp2Zr(κ2‐P,P‐Ph2P‐N‐PPh2)] ( 3 Zr ). Complexes 2 , 3 Ti , 4 Hf , and 3 Zr were characterized by X‐ray crystallography. The structures and bondings of all complexes were investigated by DFT calculations. 相似文献
16.
Insertion Reactions of Neutral Phosphidozirconocene Complexes as a Convenient Entry into Frustrated Lewis Pair Territory 下载免费PDF全文
Dr. Adrien T. Normand Dr. Gerald Kehr Prof. Pierre Le Gendre Prof. Gerhard Erker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(12):4285-4293
Neutral phosphidozirconocene complexes [Cp2Zr(PR2)Me] (Cp=cyclopentadienyl; 1a : R=cyclohexyl (Cy); 1b : R=mesityl (Mes); 1c : R=tBu) undergo insertion into the Zr?P bond by non‐enolisable carbonyl building blocks (O=CR′R′′), such as benzophenone, aldehydes, paraformaldehyde or CO2, to give [Cp2Zr(OCR′R′′PR2)Me] ( 3 – 7 ). Depending on the steric bulk around P, complexes 3 – 7 react with B(C6F5)3 to give O‐bridged cationic zirconocene dimers that display typical frustrated Lewis pair (FLP)/ambiphilic ligand behaviour. Thus, the reaction of {[Cp2Zr(μ‐OCHPhPCy2)][MeB(C6F5)3]}2 ( 10a ) with chalcone results in 1,4 addition of the Zr+/P FLP, whereas the reaction of {[Cp2Zr(μ‐OCHFcPCy2)][MeB(C6F5)3]}2 ( 11a ; Fc=(C5H4)CpFe) with [Pd(η3‐C3H5)Cl]2 yields the unique Zr?Fe?Pd trimetallic complex 13a , which has been characterised by XRD analysis. 相似文献
17.
The 2,5-dimethylthiophene (2,5-Me2T) ligand in the isomers Cp*Ir(η4-2,5-Me2T) (1) and Cp*Ir(C,S-2,5-Me2T) (2) is activated to react with the dimers Cp(CO)2M?M(CO)2Cp[M?Mo (3), W (4)] to give complexes (5,6) in which the thiophene is coordinated to three metals. Oxidation of 5 with Cp2Fe+ removes the Mo dimer to give Cp*Ir(η5-2,5-Me2T)2+. Reaction of 5 with CO displaces the Mo as [CpMo(CO)3]2 to give Cp*Ir(CO)(C,S-2,5-Me2T) (7). Ultraviolet photolysis of 1 provides a convenient route to the ring-opened isomer 2. Despite the remarkable nature of the thiophene coordination in 5 and 6, its reactivity does not suggest new pathways that would lead to the hydrodesulfurization of thiophenes. 相似文献
18.
Martin Piesch Dr. Fabian Dielmann Stephan Reichl Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(7):1518-1524
A systematic study on the reactivity of the triple-decker complex [(Cp’’’Co)2(μ,η4:η4-C7H8)] ( A ) (Cp’’’=1,2,4-tritertbutyl-cyclopentadienyl) towards sandwich complexes containing cyclo-P3, cyclo-P4, and cyclo-P5 ligands under mild conditions is presented. The heterobimetallic triple-decker sandwich complexes [(Cp*Fe)(Cp’’’Co)(μ,η5:η4-P5)] ( 1 ) and [(Cp’’’Co)(Cp’’’Ni)(μ,η3:η3-P3)] ( 3 ) (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) were synthesized and fully characterized. In solution, these complexes exhibit a unique fluxional behavior, which was investigated by variable temperature NMR spectroscopy. The dynamic processes can be blocked by coordination to {W(CO)5} fragments, leading to the complexes [(Cp*Fe)(Cp’’’Co)(μ3,η5:η4:η1-P5){W(CO)5}] ( 2 a ), [(Cp*Fe)(Cp’’’Co)(μ4,η5:η4:η1:η1-P5){(W(CO)5)2}] ( 2 b ), and [(Cp’’’Co)(Cp’’’Ni)(μ3,η3:η2:η1-P3){W(CO)5}] ( 4 ), respectively. The thermolysis of 3 leads to the tetrahedrane complex [(Cp’’’Ni)2(μ,η2:η2-P2)] ( 5 ). All compounds were fully characterized using single-crystal X-ray structure analysis, NMR spectroscopy, mass spectrometry, and elemental analysis. 相似文献
19.
Helena Brake Eugenia Peresypkina Alexander V. Virovets Martin Piesch Werner Kremer Lisa Zimmermann Christian Klimas Manfred Scheer 《Angewandte Chemie (International ed. in English)》2020,59(37):16241-16246
In a high‐yield one‐pot synthesis, the reactions of [Cp*M(η5‐P5)] (M=Fe ( 1 ), Ru ( 2 )) with I2 resulted in the selective formation of [Cp*MP6I6]+ salts ( 3 , 4 ). The products comprise unprecedented all‐cis tripodal triphosphino‐cyclotriphosphine ligands. The iodination of [Cp*Fe(η5‐As5)] ( 6 ) gave, in addition to [Fe(CH3CN)6]2+ salts of the rare [As6I8]2? (in 7 ) and [As4I14]2? (in 8 ) anions, the first di‐cationic Fe‐As triple decker complex [(Cp*Fe)2(μ,η5:5‐As5)][As6I8] ( 9 ). In contrast, the iodination of [Cp*Ru(η5‐As5)] ( 10 ) did not result in the full cleavage of the M?As bonds. Instead, a number of dinuclear complexes were obtained: [(Cp*Ru)2(μ,η5:5‐As5)][As6I8]0.5 ( 11 ) represents the first Ru‐As5 triple decker complex, thus completing the series of monocationic complexes [(CpRM)2(μ,η5:5‐E5)]+ (M=Fe, Ru; E=P, As). [(Cp*Ru)2As8I6] ( 12 ) crystallizes as a racemic mixture of both enantiomers, while [(Cp*Ru)2As4I4] ( 13 ) crystallizes as a symmetric and an asymmetric isomer and features a unique tetramer of {AsI} arsinidene units as a middle deck. 相似文献
20.
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