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1.
Treatment of Cp*(CO)Fe{kappa2(Si,P)-SiMe2PPh2} with methyl vinyl ketone gave a 1,2-addition product, Cp*(CO)Fe{kappa2(Si,P)-SiMe2OCMe(CH=CH2)PPh2}. A linear-type Cp*(CO)2FeSiMe2PPh2 also reacted with the ketone to yield a 1,4-addition product, Cp*(CO)2Fe{kappa1(Si)-SiMe2OC(Me=CHCH2PPh2}, which was further converted to a seven-membered metallacycle, Cp*(CO)Fe{kappa2(Si,P)-SiMe2OC(Me)=CHCH2PPh2}, upon photolysis. 相似文献
2.
《Journal of organometallic chemistry》1990,393(1):C6-C9
The zirconium silyl complex CpCpZr[Si(SiMe3)3]Me (1; Cp = η5-C5H5; Cp = η5-C5Me5) reacts with nitriles RCN (R = Me, CHCH2, Ph) to form the azomethine derivatives CpCpZr[NC(R)Si(SiMe3)3]Me (2, R = Me; 3, R = CHCH2; 4, R = Ph). Pyridine reacts with 1 to give a 75% yield of CpCpZr[NC5H5Si(SiMe3)3]Me (5), which results from 1,2-addition of the ZrSi bond of 1 to pyridine. These reactions provide the first examples of nitrile and pyridine insertions into a transition metal-silicon bond. The related silyl complexes Cp2Zr[Si(SiMe3)3]Me and CpCpZr[Si(SiMe3)3]Cl are much less reactive toward nitriles and pyridine. 相似文献
3.
Dr. Ana Conde Dr. Rosa Fandos Dr. Carolina Hernández Prof. Dr. Antonio Otero Dr. Ana Rodríguez Dr. María José Ruiz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(8):2319-2326
Tantalum complexes [TaCp*Me{κ4‐C,N,O,O‐(OCH2)(OCHC(CH2NMe2)?CH)py}] ( 4 ) and [TaCp*Me{κ4‐C,N,O,O‐(OCH2)(OCHC(CH2NH2)?CH)py}] ( 5 ), which contain modified alkoxide pincer ligands, were synthesized from the reactions of [TaCp*Me{κ3‐N,O,O‐(OCH2)(OCH)py}] (Cp*=η5‐C5Me5) with HC?CCH2NMe2 and HC?CCH2NH2, respectively. The reactions of [TaCp*Me{κ4‐C,N,O,O‐(OCH2)(OCHC(Ph)?CH)py}] ( 2 ) and [TaCp*Me{κ4‐C,N,O,O‐(OCH2)(OCHC(SiMe3)?CH)py}] ( 3 ) with triflic acid (1:2 molar ratio) rendered the corresponding bis‐triflate derivatives [TaCp*(OTf)2{κ3‐N,O,O‐(OCH2)(OCHC(Ph)?CH2)py}] ( 6 ) and [TaCp*(OTf)2{κ3‐N,O,O‐(OCH2)(OCHC(SiMe3)?CH2)py}] ( 7 ), respectively. Complex 4 reacted with triflic acid in a 1:2 molar ratio to selectively yield the water‐soluble cationic complex [TaCp*(OTf){κ4‐C,N,O,O‐(OCH2)(OCHC(CH2NHMe2)?CH)py}]OTf ( 8 ). Compound 8 reacted with water to afford the hydrolyzed complex [TaCp*(OH)(H2O){κ3‐N,O,O‐(OCH2)(OCHC(CH2NHMe2)?CH2)py}](OTf)2 ( 9 ). Protonation of compound 8 with triflic acid gave the new tantalum compound [TaCp*(OTf){κ4‐C,N,O,O‐(OCH2)(HOCHC(CH2NHMe2)?CH)py}](OTf)2 ( 10 ), which afforded the corresponding protonolysis derivative [TaCp*(OTf)2{κ3‐N,O,O‐(OCH2)(HOCHC(CH2NHMe2)?CH2)py}](OTf) ( 11 ) in solution. Complex 8 reacted with CNtBu and potassium 2‐isocyanoacetate to give the corresponding iminoacyl derivatives 12 and 13 , respectively. The molecular structures of complexes 5 , 7 , and 10 were established by single‐crystal X‐ray diffraction studies. 相似文献
4.
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
5.
Pietro Diversi Melania Fuligni Calogero Pinzino 《Journal of organometallic chemistry》2005,690(3):605-612
Thermolysis of the ruthenium complex [Ru(Me)Cp*(PMe2Ph)2] (1) (Cp* = η5-C5Me5) in benzene gives methane and [Ru(Ph)Cp*(PMe2Ph)2] (2), which is converted slowly to (3) through the loss of benzene. 2 was structurally characterised by single-crystal X-ray diffraction experiments. DFT calculations were performed in order to understand the behaviour of the ruthenium complex 1 towards inter- or intra-molecular C-H bond activation reactions. 相似文献
6.
《Journal of organometallic chemistry》1986,316(3):319-323
When the ferraenolate anion, (η-C5H5)(CO)2FeC(O)CH2−, is treated sequentially with methyllithium/TMEDA and benzoyl chloride, the known η3-allyl complex, (η-C5H5)(OC)Fe{η3-CH2C[OC(O)Ph]C[OC(O)Ph](CH3}, is isolated in 36% yield. When the neutral alkenyl complexes, (η-C5H5)(CO)2Fe[C(Me)CH2] and (η-C5H5)(OC)2Fe{C(OMe)CH2], were treated sequentially with methyllithium and benzoyl chloride, the η3-allyl complexes, (η-C5H5)(OC)Fe{η3-CH2C(Me)C[OC(O)Ph](Me) and (η-C5H5)(OC)Fe{η3-CH2C(OMe)C[OC(O)Ph](Me) are isolated in 8 and 11% yield, respectively. These η3-allyl ligands are presumably formed via CC coupling of the donor atoms of the formal acyl and alkenyl ligands in the intermediate complexes. 相似文献
7.
Reduction of Cp*WCl4 afforded the metalated complex (eta6-C5Me4CH2)(dmpe)W(H)Cl (1) (Cp* = C5Me5, dmpe = 1,2-bis(dimethylphosphino)ethane). Reactions with CO and H(2) suggested that 1 is in equilibrium with the 16-electron species [Cp(dmpe)WCl], and 1 was also shown to react with silanes R2SiH2 (R2 = Ph2 and PhMe) to give the tungsten(IV) silyl complexes Cp*(dmpe)(H)(Cl)W(SiHR2) (6a, R2 = Ph2; 6b, R2 = PhMe). Abstraction of the chloride ligand in 1 with LiB(C6F5)4 gave a reactive species that features a doubly metalated Cp ligand, [(eta7-C5Me3(CH2)2)(dmpe)W(H)2][B(C6F5)4] (4). In its reaction with dinitrogen, 4 behaves as a synthon for the 14-electron fragment [Cp*(dmpe)W]+, to give the dinuclear dinitrogen complex ([Cp*(dmpe)W]2(micro-N2)) [B(C6F5)4]2 (5). Hydrosilanes R2SiH2 (R2 = Ph2, PhMe, Me2, Dipp(H); Dipp = 2,6-diisopropylphenyl) were shown to react with 4 in double Si-H bond activation reactions to give the silylene complexes [Cp*(dmpe)H2W = SiR2][B(C6F5)4] (8a-d). Compounds 8a,b (R2 = Ph2 and PhMe, respectively) were also synthesized by abstraction of the chloride ligands from silyl complexes 6a,b. Dimethylsilylene complex 8c was found to react with chloroalkanes RCl (R = Me, Et) to liberate trialkylchlorosilanes RMe2SiCl. This reaction is discussed in the context of its relevance to the mechanism of the direct synthesis for the industrial production of alkylchlorosilanes. 相似文献
8.
Four‐Membered Heterometallacyclic d0 and d1 Complexes of Group 4 Metallocenes with Amidato Ligands
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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
9.
Dr. Takanori Shima Prof. Dr. Zhaomin Hou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(10):3458-3466
A new family of Y4/M2 and Y5/M heterobimetallic rare‐earth‐metal/d‐block‐transition‐metal? polyhydride complexes has been synthesized. The reactions of the tetranuclear yttrium? octahydride complex [{Cp′′Y(μ‐H)2}4(thf)4] (Cp′′=C5Me4H, 1‐C5Me4H ) with one equivalent of Group‐6‐metal? pentahydride complexes [Cp*M(PMe3)H5] (M=Mo, W; Cp*=C5Me5) afforded pentanuclear heterobimetallic Y4/M? polyhydride complexes [{(Cp′′Y)4(μ‐H)7}(μ‐H)4MCp*(PMe3)] (M=Mo ( 2 a ), W ( 2 b )). UV irradiation of compounds 2 a , b in THF gave PMe3‐free complexes [{(Cp′′Y)4(μ‐H)6(thf)2}(μ‐H)5MCp*] (M=Mo ( 3 a ), W ( 3 b )). Compounds 3 a , b reacted with one equivalent of [Cp*M(PMe3)H5] to afford hexanuclear Y4/M2 complexes [{Cp*M(μ‐H)5}{(Cp′′Y)4(μ‐H)5}{(μ‐H)4MCp*(PMe3)}] (M=Mo ( 4 a ), W ( 4 b )). UV irradiation of compounds 4 a , b provided the PMe3‐free complexes [(Cp′′Y)4(μ‐H)4{(μ‐H)5MCp*}2] (M=Mo ( 5 a ), W ( 5 b )). C5Me4Et‐ligated analogue [(Cp′′Y)4(μ‐H)4{(μ‐H)5Mo(C5Me4Et)}2] ( 5 a′ ) was obtained from the reaction of 1‐C5Me4H with [(C5Me4Et)Mo(PMe3)H5]. On the other hand, the reaction of pentanuclear yttrium? decahydride complex [{(C5Me4R)Y(μ‐H)2}5(thf)2] ( 1‐C5Me5 : R=Me; 1‐C5Me4Et : R=Et) with [Cp*M(PMe3)H5] gave the hexanuclear heterobimetallic Y5/M? polyhydride complexes [({(C5Me4R)Y}5(μ‐H)8)(μ‐H)5MCp*] ( 6 a : M=Mo, R=Me; 6 a′ : M=Mo, R=Et; 6 b : M=W, R=Me). Compound 5 a released two molecules of H2 under vacuum to give [(Cp′′Y)4(μ‐H)2{(μ‐H)4MoCp*}2] ( 7 ). In contrast, compound 6 a lost one molecule of H2 under vacuum to yield [{(Cp*Y)5(μ‐H)7}(μ‐H)4MoCp*] ( 8 ). Both compounds 7 and 8 readily reacted with H2 to regenerate compounds 5 a and 6 a , respectively. The structures of compounds 4 a , 5 a′ , 6 a′ , 7 , and 8 were determined by single‐crystal X‐ray diffraction. 相似文献
10.
Prof. Robert D. Robinson Jr. Dr. Werner Kaminsky Prof. Jeremiah J. Scepaniak 《欧洲无机化学杂志》2023,26(27):e202300369
The complexes Cp(MeIm)IrI2 and CpMe4(MeIm)IrCl2 have been prepared and subsequently methylated to form Cp(MeIm)IrMe2 and CpMe4(MeIm)IrMe2 (Cp=η5-C5H5, CpMe4=η5-C5HMe4, MeIm=1,3-dimethylimidazol-2-ylidene). We attempted unsuccessfully to use the dimethyl complexes to study C−D bond activation via methyl-group abstraction. Protonation with one equivalent of a weak acid, such as 2,6-dimethylpyridinium chloride, affords methane and IrIII methyl chloride complexes. 1H-NMR experiments show addition of pyridinium [BArF20]− (BArF20=[B(C6F5)4]−) to the dimethyl species forms [Cp(MeIm)IrMe(py)]+[BArF20]− (py=pyridine) or [CpMe4(MeIm)IrMe(py)]+[BArF20]− respectively, alongside methane, while use of the [BArF20]− salts of more bulky 2,6-dimethylpyridinium and 2,6-di-tert-butylpyridinium gave an intractable mixture. Likewise, the generation of 16 e− species [CpMe4(MeIm)IrMe]+[BArF20]− or [Cp(MeIm)IrMe]+[BarF20]− at low temperature using 2,6-dimethylpyridinium or 2,6-di-tert-butylpyridinium in thawing C6D6 or toluene-d8 formed an intractable mixture and did not lead to C−D bond activation. X-ray structures of several IrIII complexes show similar sterics as that found for the previously reported Cp* analogue. 相似文献
11.
The thermolysis of the phosphinidene complex [Cp*P[W(CO)5]2] (1) in toluene in the presence of tBuC(triple bond)CMe leads to the four-membered ring complexes [[[eta2-C(Me)C(tBu)]Cp*(CO)W(mu3-P)[W(CO)3]][eta4:eta1:eta1-P[W(CO)5]WCp*(CO)C(Me)C(tBu)]] (4) as the major product and [[W[Cp*(CO)2]W(CO)2WCp*(CO)[eta1:eta1-C(Me)C(tBu)]](mu,eta3:eta2:eta1-P2[W(CO)5]] (5). The reaction of 1 with PhC(triple bond)CPh leads to [[W(Co)2[eta2-C(Ph)C(Ph)]][(eta4:eta1-P(W(CO)5]W[Cp*(CO)2)C(Ph)C(Ph)]] (6). The products 4 and 6 can be regarded as the formal cycloaddition products of the phosphido complex intermediate [Cp*(CO)2W(triple bond)P --> W(CO)5] (B), formed by Cp* migration within the phosphinidene complex 1. Furthermore, the reaction of 1 with PhC(triple bond)CPh gives the minor product [[[eta2:eta1-C(Ph)C(Ph)]2[W(CO)4]2][mu,eta1:eta1-P[C(Me)[C(Me)]3C(Me)][C(Ph)](C(Ph)]] (7) as a result of a 1,3-dipolaric cycloaddition of the alkyne into a phosphaallylic subunit of the Cp*P moiety of 1. Compounds 4-7 have been characterized by means of their spectroscopic data as well as by single-crystal X-ray structure analysis. 相似文献
12.
Conde A Fandos R Hernández C Otero A Rodríguez A Ruiz MJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(8):2319-2326
Tantalum complexes [TaCp*Me{κ(4)-C,N,O,O-(OCH(2))(OCHC(CH(2)NMe(2))=CH)py}] (4) and [TaCp*Me{κ(4)-C,N,O,O-(OCH(2))(OCHC(CH(2)NH(2))=CH)py}] (5), which contain modified alkoxide pincer ligands, were synthesized from the reactions of [TaCp*Me{κ(3)-N,O,O-(OCH(2))(OCH)py}] (Cp* = η(5)-C(5)Me(5)) with HC≡CCH(2)NMe(2) and HC≡CCH(2)NH(2), respectively. The reactions of [TaCp*Me{κ(4)-C,N,O,O-(OCH(2))(OCHC(Ph)=CH)py}] (2) and [TaCp*Me{κ(4)-C,N,O,O-(OCH(2))(OCHC(SiMe(3))=CH)py}] (3) with triflic acid (1:2 molar ratio) rendered the corresponding bis-triflate derivatives [TaCp*(OTf)(2){κ(3)-N,O,O-(OCH(2))(OCHC(Ph)=CH(2))py}] (6) and [TaCp*(OTf)(2){κ(3)-N,O,O-(OCH(2))(OCHC(SiMe(3))=CH(2))py}] (7), respectively. Complex 4 reacted with triflic acid in a 1:2 molar ratio to selectively yield the water-soluble cationic complex [TaCp*(OTf){κ(4)-C,N,O,O-(OCH(2))(OCHC(CH(2)NHMe(2))=CH)py}]OTf (8). Compound 8 reacted with water to afford the hydrolyzed complex [TaCp*(OH)(H(2)O){κ(3)-N,O,O-(OCH(2))(OCHC(CH(2)NHMe(2))=CH(2))py}](OTf)(2) (9). Protonation of compound 8 with triflic acid gave the new tantalum compound [TaCp*(OTf){κ(4)-C,N,O,O-(OCH(2))(HOCHC(CH(2)NHMe(2))=CH)py}](OTf)(2) (10), which afforded the corresponding protonolysis derivative [TaCp*(OTf)(2){κ(3)-N,O,O-(OCH(2))(HOCHC(CH(2)NHMe(2))=CH(2))py}](OTf) (11) in solution. Complex 8 reacted with CNtBu and potassium 2-isocyanoacetate to give the corresponding iminoacyl derivatives 12 and 13, respectively. The molecular structures of complexes 5, 7, and 10 were established by single-crystal X-ray diffraction studies. 相似文献
13.
Reaction of a labile tungsten nitrile complex, [(Cp*)W(CO)2(NCMe)Me] (Cp*=η5‐C5Me5), with H3SiC(SiMe3)3 gave the hydrido(hydrosilylene) complex [(Cp*)(CO)2(H)W?Si(H){C(SiMe3)3}] ( 1a ). The hydrido(silylene) complex [(η5‐C5Me4Et)(CO)2(H)W?SiMes2] ( 2 ) (Mes=2,4,6‐Me‐C6H2) was synthesized by a similar reaction with H2SiMes2. There is a strong interligand interaction between the hydrido and silylene ligands of these complexes; this was confirmed by a neutron diffraction study of [D2] 1b , that is, the deuterido and η5‐C5Me4Et derivative of 1a . The exchange between the W? H and the Si? D groups was observed in the deuterido complex [D] 1a . This H/D exchange proceeded slowly at room temperature, but very rapidly under UV irradiation. Variable‐temperature NMR spectroscopy measurements show the dynamic behavior of carbonyl ligands in 1a . Complex 1a reacted with acetone at room temperature to give mainly a hydrosilylation product, [(Cp*)(CO)2(H)W?Si(OiPr){C(SiMe3)3}] ( 3a ), along with a siloxy complex, [(Cp*)(CO)2WO(Si(H)iPr{C(SiMe3)3})] ( 4a ). At low temperature, a different reaction, namely, α‐H abstraction, proceeded to give an equilibrium mixture of 1a and a dihydrido(silyl) complex, [(Cp*)(CO)2(H)2W(Si(H){OC(?CH2)Me}{C(SiMe3)3})] ( 5 ). 相似文献
14.
Dr. Qing You Prof. Dr. Jie Zhang Prof. Dr. Xigeng Zhou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(34):7702-7710
A new method for the modification of a silylamino ligand has been developed through mono and dual C(sp3)−H/Si−H cross-dehydrocoupling with silanes. The reaction of [LY{η2-(C,N)-CH2Si(Me2)NSiMe3}] (L=bis(2,6-diisopropylphenyl)-β-diketiminato, L′ ( 1L ′); L=tris(3,5-dimethylpyrazolyl)borate, TpMe2 ( 1TpMe2 )) with 2 equivalents of PhSiH3 in toluene gave the complexes [LY{η2-(C,N)-C(SiH2Ph)2Si(Me2)NSiMe3}] (L=L′ ( 2L’ ); L=TpMe2 ( 2TpMe2 )). Moreover, 1TpMe2 reacted with the secondary silanes Ph2SiH2 and Et2SiH2 to afford the corresponding mono C−H activation products [TpMe2Y{η2-(C,N)-CH(SiHR2)Si(Me2)NSiMe3}] (R=Ph ( 4 b ); R=Et ( 4 c )). The equimolar reaction of 1TpMe2 with PhSiH3 also produced the mono C−H activation product 4 a ([TpMe2Y{η2-(C,N)-CH(SiH2Ph)Si(Me2)NSiMe3}(thf)]). A study of their reactivity showed that 4 a facilely reacted with 2 equivalents of benzothiazole by an unusual 1,1-addition of the C=N bond of the benzothiazolyl unit to the Si−H bond to give the C−H/Si−H cross-dehydrocoupling product [(TpMe2)Y{η3-(N,N,N)-N(SiMe3)SiMe2CH2Si(Ph)(CSC6H4N)(CHSC6H4N)}] ( 5 ). These results indicate that this modification endows the silylamino ligand with novel reactivity. 相似文献
15.
Dr. Pei Jen Tiong Laura R. Groom Dr. Eric Clot Prof. Dr. Philip Mountford 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(13):4198-4216
We report a detailed study of the reactions of the Ti?NNCPh2 alkylidene hydrazide functional group in [Cp*Ti{MeC(NiPr)2}(NNCPh2)] ( 8 ) with a variety of unsaturated and saturated substrates. Compound 8 was prepared from [Cp*Ti{MeC(NiPr)2}(NtBu)] and Ph2CNNH2. DFT calculations were used to determine the nature of the bonding for the Ti?NNCPh2 moiety in 8 and in the previously reported [Cp2Ti(NNCPh2)(PMe3)]. Reaction of 8 with CO2 gave dimeric [(Cp*Ti{MeC(NiPr)2}{μ‐OC(NNCPh2)O})2] and the “double‐insertion” dicarboxylate species [Cp*Ti‐{MeC(NiPr)2}{OC(O)N(NCPh2)C(O)O}] through an initial [2+2] cycloaddition product [Cp*Ti{MeC(NiPr)2}{N(NCPh2)C(O)O}], the congener of which could be isolated in the corresponding reaction with CS2. The reaction with isocyanates or isothiocyanates tBuNCO or ArNCE (Ar=Tol or 2,6‐C6H3iPr2; E=O, S) gave either complete NNCPh2 transfer, [2+2] cycloaddition to Ti?Nα or single‐ or double‐substrate insertion into the Ti?Nα bond. The treatment of 8 with isonitriles RNC (R=tBu or Xyl) formed σ‐adducts [Cp*Ti{MeC(NiPr)2}(NNCPh2)(CNR)]. With ArF5CCH (ArF5=C6F5) the [2+2] cycloaddition product [Cp*Ti{MeC(NiPr)2}{N(NCPh2)C(ArF5)C(H)}] was formed, whereas with benzonitriles ArCN (Ar=Ph or ArF5) two equivalents of substrate were coupled in a head‐to‐tail manner across the Ti?Nα bond to form [Cp*Ti{MeC(NiPr)2}{N(NCPh2)C(Ar)NC(Ar)N}]. Treatment of 8 with RSiH3 (R=aryl or Bu) or Ph2SiH2 gave [Cp*Ti{MeC(NiPr)2}{N(SiHRR′)N(CHPh2)}] (R′=H or Ph) through net 1,3‐addition of Si? H to the N? N?CPh2 linkage of 8 , whereas reaction with PhSiH2X (X=Cl, Br) led to the Ti?Nα 1,2‐addition products [Cp*Ti{MeC(NiPr)2}(X){N(NCPh2)SiH2Ph}]. 相似文献
16.
Nisha P. Kushwah Amey Wadawale Zoya A. Starikova 《Journal of organometallic chemistry》2009,694(26):4146-4263
The reactions of [M2Cl2(μ-Cl)2(PMe2Ph)2] with mercapto-o-carboranes in the presence of pyridine afforded mono-nuclear complexes of composition, [MCl(SCb°R)(py)(PMe2Ph)] (M = Pd or Pt; Cb° = o-C2B10H10; R = H or Ph). The treatment of [PdCl2(PEt3)2] with PhCb°SH yielded trans-[Pd(SCb°Ph)2(PEt3)2] (4) which when left in solution in the presence of pyridine gave another substitution product, [Pd(SCb°Ph)2(py)(PEt3)] (5). The structures of [PdCl(SCb°Ph)(py)(PMe2Ph)] (1), [Pd(SCb°Ph)2(PEt3)2] (4) and [Pd(SCboPh)2(py)(PEt3)] (5) were established unambiguously by X-ray crystallography. The palladium atom in these complexes adopts a distorted square-planar configuration with neutral donor atoms occupying the trans positions. Thermolysis of [PdCl(SCb°)(py)(PMe2Ph)] (2) in TOPO (trioctylphosphine oxide) at 200 °C gave nanocrystals of TOPO capped Pd4S which were characterized by XRD pattern and SEM. 相似文献
17.
《Journal of organometallic chemistry》1987,322(3):351-356
Hydride or methyl abstraction from (η5-C5H5)(OC)3MH (M = Mo, W), (OC)5ReCH3 with benzyliumhexafluoroantimonate gives the complexes [(η5-C5H5)(OC)3M(OCPhH)]+SbF6− and [(OC)5Re(OCPhMe)]+SbF6−, respectively. The acetaldehyde and benzaldehyde complexes [(η5-C5H5)(OC)3M(OCRH)]+BF4− (M = Mo, W; R = Me, Ph), [(OC)5Re(OCMeH)]+Bf4− can also be formed by treating (η5-C5H5)(OC)3MFBF3 or (OC)5ReFBF3 with aldehyde. 相似文献
18.
Addition of Cationic Lewis Acids [M′Ln]+ (M′Ln = Fe(CO)2Cp, Fe(CO)(PPh3)Cp, Ru(PPh3)2Cp, Re(CO)5, Pt(PPh3)2, W(CO)3Cp to the Anionic Thiocarbonyl Complexes [HB(pz)3(OC)2M(CS)]− (M = Mo, W; pz = 3,5‐dimethylpyrazol‐1‐yl) Adducts from Organometallic Lewis Acids [Fe(CO)2Cp]+, [Fe(CO)(PPh3)Cp]+, [Ru(PPh3)2Cp]+, [Re(CO)5]+, [ Pt(PPh3)2]+, [W(CO)3Cp]+ and the anionic thiocarbonyl complexes [HB(pz)3(OC)2M(CS)]− (M = Mo, W) have been prepared. Their spectroscopic data indicate that the addition of the cations occurs at the sulphur atom to give end‐to‐end thiocarbonyl bridged complexes [HB(pz)3(OC)2MCSM′Ln]. 相似文献
19.
Muraoka T Abe K Haga Y Nakamura T Ueno K 《Journal of the American Chemical Society》2011,133(39):15365-15367
Base-stabilized silanone complex Cp*(OC)(2)W(SiMe(3)){O═SiMes(2)(DMAP)} (2) was synthesized by the reaction of (silyl)(silylene)tungsten complex Cp*(OC)(2)W(SiMe(3))(═SiMes(2)) (1) with 1 equiv of pyridine-N-oxide (PNO) in the presence of 4-(dimethylamino)pyridine (DMAP). Further oxygenation of 2 with 3 equiv of PNO at 80 °C resulted in the formation of a W-O-Si-O-Si framework to give disiloxanoxy complex Cp*(O)(2)W{OSiMes(2)(OSiMe(3))} (3). Complex 3 was also obtained by the direct reaction of complex 1 with 4 equiv of PNO at 80 °C. 相似文献
20.
R. Schemm R. Maisch M. Luksza W. Malisch 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4)
Abstract Metallation of organodichlorophosphanes RPC12 (R=Me, Ph, tBu, C5Me5) with Na[M(CO)3Cp] (M=Mo, W) in benzene yields the thermolabile Metallo(alkyl)chlorophosphanes la-g. In solution la-d show a high tendency to decompose to the corresponding metal chloride Cp(CO)3M-Cl with phosphinidene elimination. The rate of decomposition depends on the metal and the phosphorus ligand (Mo > W, Me > Ph > tBu C5Me5) 相似文献