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1.
Guohai Deng Sudip Pan Guanjun Wang Lili Zhao Mingfei Zhou Gernot Frenking 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(26):10690-10696
The preparation and spectroscopic identification of the complexes NNBe(η2-N2) and (NN)2Be(η2-N2) and the energetically higher lying isomers Be(NN)2 and Be(NN)3 are reported. NNBe(η2-N2) and (NN)2Be(η2-N2) are the first examples of covalently side-on bonded N2 adducts of a main-group element. The analysis of the electronic structure using modern methods of quantum chemistry suggests that NNBe(η2-N2) and (NN)2Be(η2-N2) should be classified as π complexes rather than metalladiazirines. 相似文献
2.
Prof. Dr. Holger Braunschweig Charlotte Brückner Dr. Mehmet Ali Celik Dr. Klaus Dück Dr. Florian Hupp Dr. Thomas Kramer Johannes Krebs Dr. Ivo Krummenacher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(31):11056-11064
Taking advantage of an improved synthesis of [Ti(η6‐C6H6)2], we report here the first examples of ansa‐bridged bis(benzene) titanium complexes. Deprotonation of [Ti(η6‐C6H6)2] with nBuLi in the presence of N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine (pmdta) leads to the corresponding 1,1′‐dilithio salt [Ti(η6‐C6H5Li)2] ? pmdta that enables the preparation of the first one‐ and two‐atom‐bridged complexes by simple salt metathesis. The ansa complexes were fully characterized (NMR spectroscopy, UV/Vis spectroscopy, elemental analysis, and X‐ray crystallography) and further studied electrochemically and computationally. Moreover, [Ti(η6‐C6H6)2] is found to react with the Lewis base 1,3‐dimethylimidazole‐2‐ylidene (IMe) to give the bent sandwich complex [Ti(η6‐C6H6)2(IMe)]. 相似文献
3.
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
4.
Guohai Deng Sudip Pan Guanjun Wang Lili Zhao Mingfei Zhou Gernot Frenking 《Angewandte Chemie (International ed. in English)》2020,59(41):18201-18207
The reactions of laser‐ablated beryllium atoms with dinitrogen and carbon monoxide mixtures form the end‐on bonded NNBeCO and side‐on bonded (η2‐N2)BeCO isomers in solid argon, which are predicted by quantum chemical calculations to be almost isoenergetic. The end‐on bonded complex has a triplet ground state while the side‐on bonded isomer has a singlet electronic ground state. The complexes rearrange to the energetically lowest lying NBeNCO isomer upon visible light excitation, which is characterized to be an isocyanate complex of a nitrene derivative with a triplet electronic ground state. A bonding analysis using a charge‐ and energy decomposition procedure reveals that the electronic reference state of Be in the NNBeCO isomers has an 2s02p2 excited configuration and that the metal‐ligand bonds can be described in terms of N2→Be←CO σ donation and concomitant N2←Be→CO π backdonation. The results demonstrate that the activation of N2 with the N?N bond being completely cleaved can be achieved via coupling with carbon monoxide mediated by a main group atom. 相似文献
5.
The synthesis, characterization and methyl methacrylate polymerization behaviors of 2‐(N‐arylimino)pyrrolide nickel complexes are described. The nickel complex [NN]2Ni ( 1 , [NN] = [2‐C(H)NAr‐5‐tBu‐C4H2N]?, Ar = 2,6‐iPr2C6H3) was prepared in good yield by the reaction of [NN]Li with trans‐[Ni(Cl)(Ph)(PPh3)2] in THF. Reaction of [NN]Li with NiBr2(DME) yielded the nickel bromide [NN]Ni(Br)[NNH] ( 2 ). Complexes 1 and 2 were characterized by 1H NMR and IR spectroscopy and elemental analysis, and by X‐ray single crystal analysis. Both complexes, upon activation with methylaluminoxane, are highly active for the polymerization of methyl methacrylate to give high molecular weight polymethylmethacrylate with narrow molecular distributions. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
6.
The coordination chemistry of platinum(II) with a series of thiosemicarbazones {R(H)C2=N3‐N2(H)‐C1(=S)‐N1H2, R = 2‐hydroxyphenyl, H2stsc; pyrrole, H2ptsc; phenyl, Hbtsc} is described. Reactions of trans‐PtCl2(PPh3)2 precursor with H2stsc (or H2ptsc) in 1 : 1 molar ratio in the presence of Et3N base yielded complexes, [Pt(η3‐ O, N3, S‐stsc)(PPh3)] ( 1 ) and [Pt(η3‐ N4, N3, S‐ptsc)(PPh3)] ( 2 ), respectively. Further, trans‐PtCl2(PPh3)2 and Hbtsc in 1 : 2 (M : L) molar ratio yielded a different compound, [Pt(η2‐ N3, S‐btsc)(η1‐S‐btsc)(PPh3)] ( 3 ). Complex 1 involved deprotonation of hydrazinic (‐N2H‐) and hydroxyl (‐OH) groups, and stsc2? is coordinating via O, N3, S donor atoms, while complex 2 involved deprotonation of hydrazinic (‐N2H‐) and ‐N4H groups and ptsc2? is probably coordinating via N4, N3, S donor atoms. Reaction of PdCl2(PPh3)2 with Hbtsc‐Me {C6H5(CH3)C2=N3‐N2(H)‐C1(=S)‐N1H2} yielded a cyclometallated complex [Pd(η3‐C, N3, S‐btsc‐Me)(PPh3)] ( 4 ). These complexes have been characterized with the help of analytical data, spectroscopic techniques {IR, NMR (1H, 31P), U.V} and single crystal X‐ray crystallography ( 1 , 3 and 4 ). The effects of substituents at C2 carbon of thiosemicarbazones on their dentacy and cyclometallation are emphasized. 相似文献
7.
On the Electronic Structure and Photochemistry of Coordinatively Unsaturated Complexes: The Case of Nickel Bis‐dinitrogen,Ni(N2)2
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Dr. Olaf Hübner Dr. Laurent Manceron Prof. Hans‐Jörg Himmel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):17025-17038
The electronic ground and excited states of the coordinatively unsaturated complex Ni(η1‐N2)2, isolated in an Ar matrix, are analyzed in detail by vibrational and electronic absorption and emission spectroscopies allied with quantum chemical calculations. The bond force constants are determined from a normal coordinate analysis and compared with those of the isoelectronic carbonyl complex. The consequences for the bond properties are discussed, and the trend in the force constants is compared with the standard formation enthalpies. The linear complex Ni(η1‐N2)2 with two terminal dinitrogen ligands can be photoisomerized to two isomeric, metastable forms Ni(η1‐N2)(η2‐N2) and Ni(η2‐N2)2, with one and two side‐on coordinated dinitrogen ligands, respectively. 相似文献
8.
The synthesis and structural characterization of two azirine rhodium(III ) complexes are described. The stabilization, N‐coordination and phenylgroup π‐stacking of the highly reactive and strained 3‐phenyl‐2H‐azirine by transition metal coordination is observed. The reaction of the dimeric complex [(η5‐C5Me5)RhCl2]2 with 3‐phenyl‐2H‐azirine (az) in CH2Cl2 at room temperature in a 1:2 molar ratio afforded the neutral mono‐azirine complex [(η5‐C5Me5)RhCl2(az)]. The subsequent reaction of [(η5‐C5Me5)RhCl2]2 with six equivalents of az and 4 equivalents of AgOTf yielded the cationic tris‐azirine complex [(η5‐C5Me5)Rh(az)3](OTf)2. After purification, all complexes have been fully characterized. The molecular structures of the novel rhodium(III ) complexes exhibit slightly distorted octahedral coordination geometries around the metal atoms. 相似文献
9.
Activation of Molecular Hydrogen by Bis(η5,η1‐pentafulvene)‐titanium Complexes – Efficient Formation of Titanium(III)hydrides
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The synthesis and crystal structures of two dinuclear titanocene hydride complexes are reported. Both complexes, namely bis(η5‐(di‐para‐tolylmethyl)cyclopentadienyl)titanium hydride dimer, [(η5‐C20H19)2Ti(μ‐H)]2 ( 2a ), and bis(η5‐2‐adamantylcyclopentadienyl)‐titanium hydride dimer, [(η5‐C15H19)2Ti(μ‐H)]2 ( 2b ), are formed via activation of molecular hydrogen by the corresponding bis(η5,η1‐pentafulvene)titanium complexes 1a and 1b at ambient temperatures and pressures in high yields. The hydride complexes 2a and 2b exhibit planar [Ti2H2] cores and, as a result of the heterolytic cleavage of molecular hydrogen, substituted Cp Ligands were formed during the reaction. 相似文献
10.
Photochemically Induced Reductive Elimination as a Route to a Zirconocene Complex with a Strongly Activated N2 Ligand
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Grant W. Margulieux Scott P. Semproni Prof. Dr. Paul J. Chirik 《Angewandte Chemie (International ed. in English)》2014,53(35):9189-9192
The zirconocene dinitrogen complex [{(η5‐C5Me4H)2Zr}2(μ2,η2,η2‐N2)] was synthesized by photochemical reductive elimination from the corresponding zirconium bis(aryl) or aryl hydride complexes, providing a high‐yielding, alkali metal‐free route to strongly activated early‐metal N2 complexes. Mechanistic studies support the intermediacy of zirconocene arene complexes that in the absence of sufficient dinitrogen promote C? H activation or undergo comproportion to formally ZrIII complexes. When N2 is in excess arene displacement gives rise to strong dinitrogen activation. 相似文献
11.
Dr. Ying Fu Dr. Rina Soni Dr. María J. Romero Dr. Ana M. Pizarro Dr. Luca Salassa Dr. Guy J. Clarkson Jessica M. Hearn Dr. Abraha Habtemariam Prof. Dr. Martin Wills Prof. Dr. Peter J. Sadler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(45):15199-15209
Four chiral OsII arene anticancer complexes have been isolated by fractional crystallization. The two iodido complexes, (SOs,SC)‐[Os(η6‐p‐cym)(ImpyMe)I]PF6 (complex 2 , (S)‐ImpyMe: N‐(2‐pyridylmethylene)‐(S)‐1‐phenylethylamine) and (ROs,RC)‐[Os(η6‐p‐cym)(ImpyMe)I]PF6 (complex 4 , (R)‐ImpyMe: N‐(2‐pyridylmethylene)‐(R)‐1‐phenylethylamine), showed higher anticancer activity (lower IC50 values) towards A2780 human ovarian cancer cells than cisplatin and were more active than the two chlorido derivatives, (SOs,SC)‐[Os(η6‐p‐cym)(ImpyMe)Cl]PF6, 1 , and (ROs,RC)‐[Os(η6‐p‐cym)(ImpyMe)Cl]PF6, 3 . The two iodido complexes were evaluated in the National Cancer Institute 60‐cell‐line screen, by using the COMPARE algorithm. This showed that the two potent iodido complexes, 2 (NSC: D‐758116/1) and 4 (NSC: D‐758118/1), share surprisingly similar cancer cell selectivity patterns with the anti‐microtubule drug, vinblastine sulfate. However, no direct effect on tubulin polymerization was found for 2 and 4 , an observation that appears to indicate a novel mechanism of action. In addition, complexes 2 and 4 demonstrated potential as transfer‐hydrogenation catalysts for imine reduction. 相似文献
12.
Experimental and Computational Studies on the Reactivity of a Terminal Thorium Imidometallocene towards Organic Azides and Diazoalkanes
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Dr. Wenshan Ren Enwei Zhou Bo Fang Dr. Guohua Hou Prof. Guofu Zi Prof. De‐Cai Fang Dr. Marc D. Walter 《Angewandte Chemie (International ed. in English)》2014,53(42):11310-11314
The reaction of the base‐free terminal thorium imido complex [{η5‐1,2,4‐(Me3C)3C5H2}2Th?N(p‐tolyl)] ( 1 ) with p‐azidotoluene yielded irreversibly the tetraazametallacyclopentene [{η5‐1,2,4‐(Me3C)3C5H2}2Th{N(p‐tolyl)N?N? N(p‐tolyl)}] ( 2 ), whereas the bridging imido complex [{[η5‐1,2,4‐(Me3C)3C5H2]Th(N3)2}2{μ‐N(p‐tolyl)}2][(n‐C4H9)4N]2 ( 3 ) was isolated from the reaction of 1 with [(n‐C4H9)4N]N3. Unexpectedly, upon the treatment of 1 with 9‐diazofluorene, the NN bond was cleaved, an N atom was transferred, and the η2‐diazenido iminato complex [{η5‐1,2,4‐(Me3C)3C5H2}2Th{η2‐[N?N(p‐tolyl)]}{N?(9‐C13H8)}] ( 4 ) was formed. In contrast, the reaction of 1 with Me3SiCHN2 gave the nitrilimido complex [{η5‐1,2,4‐(Me3C)3C5H2}2Th{NH(p‐tolyl)}{N2CSiMe3}] ( 5 ), which slowly converted into [{η5‐1,2,4‐(Me3C)3C5H2}{η5:κ‐N‐1,2‐(Me3C)2‐4‐CMe2(CH2NN?CHSiMe3)C5H2}Th{NH(p‐tolyl)}] ( 6 ) by intramolecular C? H bond activation. The experimental results are complemented by density functional theory (DFT) studies. 相似文献
13.
A series of molecular homo and heteroleptic zinc and magnesium compounds with aminophenolate ligands [(µ,η2-L2)ZnEt]2 ( 1 ), [(η2-L2)Zn(µ-BnO)]2 ( 2 ), [Zn(η2-L2)2] ( 3 ), [Zn(η2-L3)2] ( 4 ), [Mg(η2-L3)2] ( 5 ) (L2-H = N-[methylene(2-hydroxy-3,5-di-tert-butylphenyl)]-N-methyl-N-cyclohexylamine, L3-H = N-[methylene(2-hydroxy-3,5-di-tert-butylphenyl)]-N-methyl-N-methyl-1,3-dioxolaneamine) have been prepared and characterized. The homoleptic complexes 3–5 are most probably a mixture of diastereoisomers that in solution show an interesting dynamics which plays an important role in their catalytic behavior. The complexes 2 – 5 are efficient initiators in ring-opening polymerization (ROP) of lactides to produce polymers with desired molecular weight and narrow polydispersity. 相似文献
14.
Dr. Tetsuya Fukuda Dr. Hisako Hashimoto Prof. Dr. Shigeyoshi Sakaki Prof. Dr. Hiromi Tobita 《Angewandte Chemie (International ed. in English)》2016,55(1):188-192
Treatment of pyridine‐stabilized silylene complexes [(η5‐C5Me4R)(CO)2(H)W?SiH(py)(Tsi)] (R=Me, Et; py=pyridine; Tsi=C(SiMe3)3) with an N‐heterocyclic carbene MeIiPr (1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene) caused deprotonation to afford anionic silylene complexes [(η5‐C5Me4R)(CO)2W?SiH(Tsi)][HMeIiPr] (R=Me ( 1‐Me ); R=Et ( 1‐Et )). Subsequent oxidation of 1‐Me and 1‐Et with pyridine‐N‐oxide (1 equiv) gave anionic η2‐silaaldehydetungsten complexes [(η5‐C5Me4R)(CO)2W{η2‐O?SiH(Tsi)}][HMeIiPr] (R=Me ( 2‐Me ); R=Et ( 2‐Et )). The formation of an unprecedented W‐Si‐O three‐membered ring was confirmed by X‐ray crystal structure analysis. 相似文献
15.
The crystalline compounds NSi(NN)Si(NN)CR [R = But ( 2 a ), Ad ( 2 b )], (NN)Si(But)CN ( 3 ), ButSi(NN)Si(NN)CN ( 4 ), AdNSi(NN)Si(NN) ( 5 ), AdNN=NN(Ad)Si(NN) ( 6 ), (NN)Si(N3)N(SiMe3)2 ( 7 ) and Me3SiNSi(NN)Si(NN)(thf) ( 8 ) were obtained in good yield under mild conditions from Si[(NCH2But)2C6H4‐1,2] [≡ Si(NN)] and the appropriate reagent RCN, ButNC and R′N3. The compounds 2 – 8 were characterised by microanalysis, multinuclear NMR and (not 8 ) mass spectra, as well as for 2 a , 4 and 7 single crystal X‐ray diffraction data. The results are placed in context of data in the literature on reactions of especially Si[N(But)CH=]2, (SiBut2)3, Mes2Si=SiMes2 with (where available) a nitrile, isonitrile or azide. Reaction pathways are discussed. 相似文献
16.
Kazushi Mashima 《Macromolecular Symposia》2000,159(1):69-76
Half‐metallocene diene complexes of niobium and tantalum catalyzed three‐types of polymerization: (1) the living polymerization of ethylene by niobium and tantalum complexes, MCl2(η4‐1,3‐diene)(η5‐C5R5) ( 1‐4 ; M = Nb, Ta; R = H, Me) combined with an excess of methylaluminoxane; (2) the stereoselective ring opening metathesis polymerization of norbornene by bis(benzyl) tantalum complexes, Ta(CH2Ph)2(η4‐1,3‐butadiene)(η5‐C5R5) ( 11 : R = Me; 12 : R = H) and Ta(CH2Ph)2(η4‐o‐xylylene)(η5‐C5Me5) ( 16 ); and (3) the polymerization of methyl methacrylate by butadiene‐diazabutadiene complexes of tantalum, Ta(η2‐RN=CHCH=NR)(η4‐1,3‐butadiene)(η5‐C5Me5) ( 25 : R = p‐methoxyphenyl; 26 : R = cyclohexyl) in the presence of an aluminum compound ( 24 ) as an activator of the monomer. 相似文献
17.
Tuning the Excited State of Water‐Soluble IrIII‐Based DNA Intercalators that are Isostructural with [RuII(NN)2(dppz)] Light‐Switch Complexes
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Sasha Stimpson Dan R. Jenkinson Andrew Sadler Dr. Mark Latham Dr Ashley Wragg Dr. Anthony J. H. M. Meijer Dr. Jim A. Thomas 《Angewandte Chemie (International ed. in English)》2015,54(10):3000-3003
The synthesis of two new IrIII complexes which are effectively isostructural with well‐established [Ru(NN)2(dppz)]2+ systems is reported (dppz=dipyridophenazine; NN=2,2′‐bipyridyl, or 1,10‐phenanthroline). One of these IrIII complexes is tricationic and has a conventional N6 coordination sphere. The second dicationic complex has a N5C coordination sphere, incorporating a cyclometalated analogue of the dppz ligand. Both complexes show good water solubility. Experimental and computational studies show that the photoexcited states of the two complexes are very different from each other and also differ from their RuII analogues. Both of the complexes bind to duplex DNA with affinities that are two orders of magnitude higher than previously reported Ir(dppz)‐based systems and are comparable with RuII(dppz) analogues. 相似文献
18.
Doyle J. Cassar Dr. Gennadiy Ilyashenko Dr. Muhammad Ismail James Woods Dr. David L. Hughes Dr. Christopher J. Richards 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(52):17951-17962
The reaction of (η5‐(N,N‐dimethylaminomethyl)cyclopentadien‐yl)(η4‐tetraphenylcyclobutadiene)cobalt with sodium tetrachloropalladate and (R)‐N‐acetylphenylalanine gave planar chiral palladacycle di‐μ‐chloridebis[(η5‐(Sp)‐2‐(N,N‐dimethylaminomethyl)cyclopentadienyl,1‐C,3′‐N)(η4‐tetraphenylcyclobutadiene)cobalt]dipalladium [(Sp)‐Me2‐CAP‐Cl] in 92 % ee and 64 % yield. Enantiopurity (>98 % ee) was achieved by purification of the monomeric (R)‐proline adducts and conversion back to the chloride dimer. Treatment with AgOAc gave (Sp)‐Me2‐CAP‐OAc which was applied to asymmetric transcyclopalladation (up to 78 % ee). The (R)‐N‐acetylphenylalanine mediated palladation methodology was applicable also to the corresponding N,N‐diethyl (82 % ee, 39 % yield) and pyrrolidinyl (>98 % ee, 43 % yield) cobalt sandwich complexes. A combination of 5 mol % of the latter [(Sp)‐Pyrr‐CAP‐Cl] and AgNO3 (3.8 equiv) is a catalyst for the allylic imidate rearrangement of an (E)‐N‐aryltrifluoroacetimidate (up to 83 % ee), and this catalyst system is also applicable to the rearrangement of a range of (E)‐trichloroacetimidates (up to 99 % ee). This asymmetric efficiency combined with the simplicity of catalyst synthesis provides accessible solutions to the generation of non‐racemic allylic amine derivatives. 相似文献
19.
Sergio A. Moya Juana Gajardo Juan C. Araya Jaime J. Cornejo Véronique Guerchais Hubert Le Bozec J. Carles Bayón Alvaro J. Pardey Pedro Aguirre 《应用有机金属化学》2008,22(8):471-478
Novel ruthenium (II) complexes were prepared containing 2‐phenyl‐1,8‐naphthyridine derivatives. The coordination modes of these ligands were modified by addition of coordinating solvents such as water into the ethanolic reaction media. Under these conditions 1,8‐naphthyridine (napy) moieties act as monodentade ligands forming unusual [Ru(CO)2Cl2(η1‐2‐phenyl‐1,8‐naphthyridine‐ kN )(η1‐2‐phenyl‐1,8‐naphthyridine‐kN′)] complexes. The reaction was reproducible when different 2‐phenyl‐1,8‐naphthyridine derivatives were used. On the other hand, when dry ethanol was used as the solvent we obtained complexes with napy moieties acting as a chelating ligand. The structures proposed for these complexes were supported by NMR spectra, and the presence of two ligands in the [Ru(CO)2Cl2(η1‐2‐phenyl‐1,8‐naphthyridine‐ kN )(η1‐2‐phenyl‐1,8‐naphthyridine‐kN′)] type complexes was confirmed using elemental analysis. All complexes were tested as catalysts in the hydroformylation of styrene showing moderate activity in N,N′‐dimethylformamide. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
20.
Dr. Burgert Blom Prof. Dr. Matthias Driess Daniel Gallego Prof. Dr. Shigeyoshi Inoue 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(42):13355-13360
A series of unprecedented bis‐silylene titanium(II) complexes of the type [(η5‐C5H5)2Ti(LSiX)2] (L=PhC(NtBu)2; X=Cl, CH3, H) has been prepared using a phosphane elimination strategy. Treatment of the [(η5‐C5H5)2Ti(PMe3)2] precursor ( 1 ) with two molar equivalents of the N‐heterocyclic chlorosilylene LSiCl ( 2 ), results in [(η5‐C5H5)2Ti(LSiCl)2] ( 3 ) with concomitant PMe3 elimination. The presence of a Si? Cl bond in 3 enabled further functionalization at the silicon(II) center. Accordingly, a salt metathesis reaction of 3 with two equivalents of MeLi results in [(η5‐C5H5)2Ti(LSiMe)2] ( 4 ). Similarly, the reaction of 3 with two equivalents of LiBHEt3 results in [(η5‐C5H5)2Ti(LSiH)2] ( 5 ), which represents the first example of a bis‐(hydridosilylene) metal complex. All complexes were fully characterized and the structures of 3 and 4 elucidated by single‐crystal X‐ray diffraction analysis. DFT calculations of complexes 3 – 5 were also carried out to assess the nature of the titanium–silicon bonds. Two σ and one π‐type molecular orbital, delocalized over the Si‐Ti‐Si framework, are observed. 相似文献