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1.
The lithiation of 4-heterosubstituted dibenzothiins 1 (phenoxathiin, phenothiazine and thianthrene) with lithium and a catalytic amount of 4,4′-di-tert-butylbiphenyl (DTBB, 7.5% molar) in THF at temperatures ranging from −90 to −78°C gives the corresponding functionalised organolithium intermediate I, which by reaction with different electrophiles [H2O, D2O, ButCHO, PhCHO, Ph(CH2)2CHO, Me2CO, Et2CO, (CH2)5CO, (CH2)7CO] at the same temperature, followed by hydrolysis, gives the expected functionalised thiols 2. Cyclisation of some thiols 2 under acidic conditions leads to the corresponding seven-membered dibenzo heterocycles 5. In the case of thianthrene 1c, after addition of a carbonyl compound as the first electrophile [MeCHO, ButCHO, Me2CO, Et2CO, (CH2)5CO], the corresponding intermediate II can be lithiated again and react with a second electrophile. Diols 3 are obtained after hydrolysis when a carbonyl compound [ButCHO, PhCHO, Ph(CH2)2CHO, Me2CO, Et2CO, (CH2)5CO] is used as the second electrophile. Acidic cyclisation of diols 3 gives substituted phthalans 6 in almost quantitative yields. Finally, in the case of using carbon dioxide as the second electrophile, phthalides 4 are obtained after acidic hydrolysis. 相似文献
2.
The reaction of 2,2-diphenylmethylenecyclopropane (5) with an excess of lithium and a catalytic amount of DTBB (4 mol %) in THF at −78 °C leads to the formation of dilithiated species 6-8 by reductive opening of the cyclopropane ring. Further reaction of these intermediates with different electrophiles [E = H2O, D2O, CH2CMeCH2Cl, Me3SiCl, Me3SiCH2Cl, t-BuCHO, Me2CO, Et2CO, n-Pr2CO, i-Pr2CO, t-Bu2CO, (CH2)5CO, Ph2CO and adamantanone] is highly regioselective, yielding exclusively the corresponding products 9, after hydrolysis with water. However, when 3-chloro-2-(chloromethyl)propene (14) is used as a dielectrophile, the cyclisation to give a six-membered ring takes place through intermediate 6, giving compound 16 as the only reaction product. 相似文献
3.
The 4,4′di-tert-butylbiphenyl (DTBB)-catalysed lithiation of dihydrodibenzothiepine (1) at −78 °C for 30 min followed by reaction with a carbonyl compound [tBuCHO, Ph(CH2)2CHO, PhCHO, (n-C5H11)2CO, (CH2)5CO, (CH2)7CO, (−)-menthone] at the same temperature leads, after hydrolysis with 3 M hydrochloric acid, to sulphanyl alcohols 2. If after addition of a carbonyl compound as the first electrophile [Me2CO, (CH2)5CO, (−)-menthone], the resulting dianion of type II is allowed to react at room temperature for 30 min, a second lithiation takes place to give an intermediate of type III, which by reaction with a second electrophile [Me2CO, Et2CO, (CH2)5CO, ClCO2Et], yields, after hydrolysis, difunctionalised byphenyls 4. The cyclisation of the sulphanyl alcohol 2c under acidic conditions yields the eight-membered sulphur containing heterocycle 3. The lithiation of dihydrodinaphthoheteroepines 7 and 10 with 2.2 equiv of lithium naphthalenide in THF at −78 °C followed by reaction with different electrophiles [H2O, D2O, tBuCHO, Me2CO, Et2CO, (CH2)4CO, (CH2)5CO] at the same temperature leads, after hydrolysis, to unsymmetrically 2,2′-disubstituted binaphthyls 9 and 12, respectively. When the lithiation is performed with an excess of lithium in the presence of a catalytic amount of DTBB (10% molar), a double reductive cleavage takes place to give the dianionic intermediate VII, which by reaction with different electrophiles [H2O, Me2CO, Et2CO, (CH2)4CO, (CH2)5CO], followed by hydrolysis with water, yields symmetrically 2,2′-disubstituted binaphthyls 8 and 11. In the case of starting from (R)- or (S)-dihydrodinaphthoheteroepines 7 and 10, these methodologies allow us to prepare enantiomerically pure compounds 8, 11 and 12. 相似文献
4.
Dmitrii P. Krut’ko Maxim V. Borzov Edward N. Veksler Andrei V. Churakov 《Journal of organometallic chemistry》2005,690(17):4036-4048
Synthetic routines for a new ligand C5Me4CH2CH2PMe2 (2b) in forms of its Li- (2b-Li), Na- (2b-Na) salts and in the CH-form (2b-H), as well as for silanes Me3Si-C5H4CH2CH2PMe2 (3a) and Me3Si-C5Me4CH2CH2PMe2 (3b) have been developed. On the basis of it, new half-sandwich [η5:η1-κP-C5H4CH2CH2PMe2]ZrCl3 (4a), [η5:η1-κP-C5Me4CH2CH2PMe2]ZrCl3 (4b) and sandwich [η5-C5Me4CH2CH2PMe2]2ZrCl2 (5), [η5-C5Me4CH2CH2PMe2][η5-C5Me5]ZrCl3 (6) complexes of Zr(IV) have been prepared and characterized. Along with them, the first example of X-ray structurally characterized dinuclear Zr(IV) complex incorporating both sandwich (6) and half-sandwich (4b) moieties linked one to another by means of Zr ← P coordination bond 7, has been described. Formation of an analogously organized trinuclear complex 8, built from one sandwich fragment of 5 and two half-sandwich fragments of 4b was proved by NMR spectroscopy methods. Molecular structures of half-sandwich complexes in their solvent-free dimeric forms (4a and 4b) and as 1:1 adducts with THF (4a-THF and 4b-THF) along with those of dinuclear complex 7 have been established by X-ray diffraction analyses. The dynamic behavior for di- and trinuclear complexes 7 and 8, due to the intermolecular dissociation-coordination of the Me2P-groups in THF-d8 solutions has been studied by variable-temperature NMR spectroscopy. 相似文献
5.
Bettina Bach 《Journal of organometallic chemistry》2004,689(2):429-437
Decamethyl-1,3-diboraruthenocene [(η5-C5Me5)Ru{η5-(CMe)3(BMe)2}] (1) reacts with cyclo-octasulfur in hexane to give [(η5-C5Me5){η5-(CMe)3(BMe)2}RuS] (3), which may also be obtained from 1 and propylene sulfide. 1 reacts with H2S to form the ruthenathiacarboranyl complex [(η5-C5Me5)Ru{η4-(CMe)3(BMe)2S}] (6), for which a nido-structure is proposed. The isomeric compounds 3 and 6 have different stabilities: 3 loses sulfur and unexpectedly the closo-cluster [(η5-C5Me5)2Ru2H(CMe)3(BMe)2] (4) is formed with hydrogen bridging the basal and apical Ru centers. Reaction of 1 with carbonylsulfide (COS) yields the dinuclear ruthenium compound [(η5-C5Me5)Ru{η5-(CMe)3(BMe)2(S)(COBMe)}]2 (7) in which two B-O groups bridge two ruthenium complexes. Its formation results from a complex reaction sequence: sulfur inserts into the diborolyl ring and the ligand CO forms an oxygen-boron bridge to a second molecule, followed by insertion of the carbonyl carbon into the double bond of the diboraheterocycle. Carbon disulfide reacts with 1 to give the dinuclear complex 8 with two CS2 molecules connecting the ruthenium centers. When 1 and P4 are heated in toluene, the sandwich 9 is obtained by formal insertion of a P-H group into the diborolyl ring of 1 and the triple-decker [{η5-(C5Me5)Ru}2{μ-(MeC)3P(MeB)2} (10) is detected in the mass spectrum. The phosphaalkyne PCtBu inserts into 1 to give the ruthenaphosphacarborane [(η5-C5Me5)Ru{(CMe)2(BMe)(PCtBu)(CMe)(BMe)}] (11) in high yield. Phosphanes react with 1 to give weak donor-acceptor complexes 1 · PH2R (12) (R=Ph, H). The compositions of the compounds are deduced from spectroscopic and analytical data and are confirmed for 4 and 7 by X-ray structural analyses. 相似文献
6.
Fernando Godoy Alejandra Gómez A. Hugo Klahn 《Journal of organometallic chemistry》2010,695(3):346-4353
The fulvene complexes [(η6-C5Me4CH2)Re(CO)2(R)] (1a, RI; 1b, RC6F5) react at the exocyclic methylene carbon with a vinylmagnesium bromide solution to produce the anionic species [(η5-C5Me4CH2CHCH2)Re(CO)2(R)]−. Protonation with HCl at 0 °C produces the hydride complexes [trans-(η5-C5Me4CH2CHCH2)Re(CO)2(R)(H)] (2a, RI; 2b, RC6F5). Thermolysis of an hexane solution of the iodo-hydride (2a) under a CO atmosphere yields the complex [(η5-C5Me4CH2CHCH2)Re(CO)3] (3) and [Re(CO)5I] as by-product. Thermolysis of 2b produced three new products, mainly the chelated complex [(η5:η2-C5Me4CH2CHCH2)Re(CO)2] (4) and complex 3, with a non-coordinated olefin group, in moderated yield, and traces of [Re(CO)5(C6F5)]. Thermolysis of an hexane solution of 2 in presence of an excess of PMe3, afforded the phosphine derivative [(η5-C5Me4CH2CHCH2)Re(CO)2(PMe3)] (5). All the complexes were characterized by IR, 1H, 13C and 31P NMR spectroscopies and mass spectrometry. The molecular structure of 4 has also been determined. The molecule exhibits a formal three-legged piano-stool structure, with two CO groups, and the third position corresponding to the η2-coordination of the propenyl side arm of the η5-C5Me4 ring. 相似文献
7.
Hisako Hashimoto Kazuyoshi Kurashima Hiroshi Ogino 《Journal of organometallic chemistry》2004,689(9):1481-1495
A phosphido-bridged unsymmetrical diiron complex (η5-C5Me5)Fe2(CO)4(μ-CO)(μ-PPh2) (1) was synthesized by a new convenient method; photo-dissociation of a CO ligand from (η5-C5Me5)Fe2(CO)6(μ-PPh2) (2) that was prepared by the reaction of Li[Fe(CO)4PPh2] with (η5-C5Me5)Fe(CO)2I. The reactivity of 1 toward various alkynes was studied. The reaction of 1 with tBuCCH gave a 1:1 mixture of two isomeric complexes (η5-C5Me5)Fe2(CO)3(μ-PPh2)[μ-CHC(tBu)C(O)] (3) containing a ketoalkenyl ligand. The reactions of 1 with other terminal alkynes RCCH (R=H, CO2Me, Ph) afforded complexes incorporating one or two molecules of alkynes and a carbonyl group. The principal products were dinuclear complexes bridged by a new phosphinoketoalkenyl ligand, (η5-C5Me5)Fe2(CO)3(μ-CO)[μ-CR1CR2C(O)PPh2] (4a: R1=H, R2=H; 4b: R1=CO2Me, R2=H; 4c: R1=H, R2=Ph). In the cases of alkynes RCCH (R=H, CO2Me), dinuclear complexes having a new ligand composed of two molecules of alkynes, a carbonyl group, and a phosphido group; i.e. (η5-C5Me5)Fe2(CO)3[μ-CRCHCHCRC(O)PPh2] (5a: R=H; 5b: R=CO2Me), were also obtained. In all cases, mononuclear complexes, (η5-C5Me5)Fe(CO)[CR1CR2C(O)PPh2] (6a: R1=H, R2=H; 6b: R1=H, R2=CO2Me; 6c: R1=H, R2=Ph) were isolated in low yields. The structures of 1, 4c, 5b, and 6a were confirmed by X-ray crystallography. The detailed structures of the products and plausible reaction mechanisms are discussed. 相似文献
8.
Cecilia Gómez 《Tetrahedron》2007,63(22):4655-4662
The reaction of phenylcyclopropane (1) with an excess of lithium and a catalytic amount of DTBB (2.5% molar) in THF at room temperature, followed by treatment with an electrophile [Me3SiCl, PhMe2SiCl, t-BuCHO, PhCHO, Me2CO, Et2CO, (CH2)5CO, adamantan-2-one, i-Pr2CO, di(cyclopropyl)ketone] and final hydrolysis with water leads to allylic products 10 or 11 depending on the structure of the electrophile: whereas for chlorosilanes or crowded ketones γ-products 11 are isolated, for aldehydes and non-congested ketones α-products 10 are formed. The application of the same protocol to 1,1-diphenylcyclopropane (7) leads to a mixture of products 13-15 resulting from the introduction of one or two electrophilic fragments to the open-chain mono- or dilithiated intermediate: also in this case the regiochemistry of the reaction is governed by steric reasons. 相似文献
9.
The complex [(η6-p-cymene)Ru(μ-Cl)Cl]21 reacts with pyrazole ligands (3a-g) in acetonitrile to afford the amidine derivatives of the type [(η6-p-cymene)Ru(L)(3,5-HRR′pz)](BF4)2 (4a-f), where L = {HNC(Me)3,5-RR′pz}; R, R′ = H (4a); H, CH3 (4b); C6H5 (4c); CH3, C6H5 (4d) OCH3 (4e); and OC2H5 (4f), respectively. The ligand L is generated in situ through the condensation of 3,5-HRR′pz with acetonitrile under the influence of [(η6-p-cymene)RuCl2]2. The complex [(η6-C6Me6)Ru(μ-Cl)Cl]22 reacts with pyrazole ligands in acetonitrile to yield bis-pyrazole derivatives such as [(η6-C6Me6)Ru (3,5-HRR′pz)2Cl](BF4) (5a-b), where R, R′ = H (5a); H, CH3 (5b), as well as dimeric complexes of pyrazole substituted chloro bridged derivatives [{(η6-C6Me6)Ru(μ-Cl) (3,5-HRR′pz)}2](BF4)2 (5c-g), where R, R′ = CH3 (5c); C6H5 (5d); CH3, C6H5 (5e); OCH3 (5f); and OC2H5 (5g), respectively. These complexes were characterized by FT-IR and FT-NMR spectroscopy as well as analytical data. The molecular structures1 of representative complexes [(η6-C6Me6)Ru{3(5)-Hmpz}2Cl]+5b, [(η6-C6Me6)Ru(μ-Cl)(3,5-Hdmpz)]22+5c and [(η6-C6Me6)Ru(μ-Cl){3(5)Me,5(3)Ph-Hpz}]22+5e were established by single crystal X-ray diffraction studies. 相似文献
10.
Hemant K. Sharma 《Journal of organometallic chemistry》2010,695(8):1168-8007
Treatment of PhMe2SiCH2GeMe3 (1) with t-BuLi followed by addition of Me3ECl, E = Sn, Pb, results in the formation of phenylsilyl(germyl)stannyl- and phenylsilyl(germyl)plumbyl-methanes, PhMe2Si(Me3Ge)(EMe3)CH, E = Sn (2), Pb (3). The thermal reaction of 1, 2 and 3 with Cr(CO)6 yields the corresponding aryl-Cr(CO)3 analogs, {(η6-C6H5)Cr(CO)3}Me2Si(Me3Ge)CH2 (4) and {(η6-C6H5)Cr(CO)3}Me2Si(Me3Ge)(EMe3)CH, E = Sn (5), Pb (6). The thermal treatment of 2 with Cr(CO)6 in a wet THF/di-n-butyl ether mixture results in the formation of the arenechromiumtricarbonyl silanol {(η6-C6H5)Cr(CO)3}Me2SiOH (7) which exhibits amphiphilic character, forming H-bonded chains in the solid state in a head-to-head arrangement of the areneCr(CO)3 units. 相似文献
11.
Dmitrii P. Krut’ko Roman S. Kirsanov Maxim V. Borzov Andrei V. Churakov 《Journal of organometallic chemistry》2007,692(7):1465-1471
Half-sandwich [η5:η1-κN-C5Me4CH2-(2-C5H4N)]MCl3 (M = Ti (4), Zr (5)) and sandwich [η5-C5Me4CH2-(2-C5H4N)][η5-C5Me5]ZrCl2 (6) ring-peralkylated complexes have been prepared and characterized. Evidence of the intramolecular coordination of the side-chain pyridyl group both in 4 and 5 in solutions is provided by NMR spectroscopy data. Crystal structure of an adduct 5-py with one molecule of pyridine has been established by X-ray diffraction analysis. 相似文献
12.
Dmitrii P. Krut’ko Maxim V. Borzov Mikhail Yu. Antipin 《Journal of organometallic chemistry》2004,689(3):595-604
A novel half-sandwich Zr(IV) complex [η5:η1-N-C5(CH3)4CH2CH2N(CH3)2]ZrCl3 (6) together with zirconocene dichlorides [η5-C5(CH3)4CH2CH2N(CH3)2][η5-C5(CH3)5]ZrCl2 (4) and [η5-C5(CH3)4CH2CH2N(CH3)2]2ZrCl2 (5) have been prepared. Complex 6 has been isolated and characterized in three different forms, namely, as an adduct with THF 6a, an adduct with tetrahydrothiophene 6b, and a solvent-free form 6c. Molecular structures of complexes 4, 6b, and 6c have been established by X-ray diffraction analysis. Complex 6c has been shown to be a monomeric solvent-free half sandwich Zr(IV) complex. The dynamic behavior of complex 6a in a non-solvating medium (an equilibrium between 6a and 6c along with a degenerate interconversion of the Zr-Ccp-CH2-CH2-N(CH3)2-(Zr) pseudo-five-member metallacycle) have been studied by the variable-temperature 1H and 13C{1H} NMR spectroscopy. The activation parameters for the degenerate five-member cycle interconversion have been elucidated. 相似文献
13.
Sergey A. Belov Dmitrii P. Krut’ko Dmitrii A. Lemenovskii Judith A.K. Howard 《Journal of organometallic chemistry》2008,693(10):1912-1918
Novel half-sandwich [C9H5(SiMe3)2]ZrCl3 (3) and sandwich [C9H5(SiMe3)2](C5Me4R)ZrCl2 (R = CH3 (1), CH2CH2NMe2 (2)) complexes were prepared and characterized. The reduction of 2 by Mg in THF lead to (η5-C9H5(SiMe3)2)[η5:η2(C,N)-C5Me4CH2CH2N(Me)CH2]ZrH (7). The structure of 7 was proved by NMR spectroscopy data. Hydrolysis of 2 resulted in the binuclear complex ([C5Me4CH2CH2NMe2]ZrCl2)2O (6). The crystal structures of 1 and 6 were established by X-ray diffraction analysis. 相似文献
14.
The reaction of biphenyl (1) with an excess of lithium in THF at room temperature leads to a solution of the corresponding dianion (I), which by successive reactions with an alkyl fluoride [E1 = n-C8H17F, c-C5H9CH2F, CH2CH(CH2)4F] at 0 °C and another electrophile [E2 = n-C4H9Br, Et2CO, Me2C(O)CH2, i-Pr3SiCl] at −78 °C yields the corresponding 1,4-disubstituted 1,4-dihydrobiphenyls 3 in a regioselective manner, as mixtures of cis- and trans-isomers. The diastereomers of 3 are separated by column chromatography. 相似文献
15.
Paul F. Hudrlik Donghua Dai Anne M. Hudrlik 《Journal of organometallic chemistry》2006,691(6):1257-1264
Reactions of 1,4-dilithiobutadienes (from 1,4-diiodo-1,2,3,4-tetraethylbutadiene (1) and 2,2′-dibromobiphenyl (7) with t-BuLi) with Me3SiCl gave siloles (3 and 9a) as the major products. No evidence for a disilylated butadiene was obtained. Use of higher molecular weight chlorosilanes ((allyl)Me2SiCl, BnMe2SiCl, and PhMe2SiCl) with dibromide 7 gave dimethylsilole 9a and a silane (10a, 10b, or 10c) resulting from trapping of the organic group by the chlorosilane. 相似文献
16.
Brendan J. Liddle 《Journal of organometallic chemistry》2010,695(1):53-1658
A series of tricarbonyl rhenium(I) and manganese(I) complexes of the electroactive 2-(pyrazolyl)-4-toluidine ligand, H(pzAnMe), has been prepared and characterized including by single crystal X-ray diffraction studies. The reactions between H(pzAnMe) and M(CO)5Br afford fac-MBr(CO)3[H(pzAnMe)] (M = Mn, 1a; Re, 1b) complexes. The ionic species {fac-M(CH3CN)(CO)3[H(pzAnMe)]}(PF6) (M = Mn, 2a; Re, 2b) were prepared by metathesis of 1a or 1b with TlPF6 in acetonitrile. Complexes 1a and 1b partly ionize to {M(CH3CN)(CO)3[H(pzAnMe)]+}(Br−) in CH3CN but retain their integrity in less donating solvents such as acetone or CH2Cl2. Each of the four metal complexes reacts with (NEt4)(OH) in CH3CN to give poorly-soluble crystalline [fac-M(CO)3(μ-pzAnMe)]2 (M = Mn, 3a; Re, 3b). The solid state structures of 3a and 3b are of centrosymmetric dimeric species with bridging amido nitrogens and with pyrazolyls disposed trans- to the central planar M2N2 metallacycle. In stark contrast to the diphenylboryl derivatives, Ph2B(pzAnMe), none of the tricarbonyl group 7 metal complexes are luminescent. 相似文献
17.
Heinrich Lang Bettina Lühmann Roy Buschbeck 《Journal of organometallic chemistry》2004,689(22):3598-3603
A straightforward method for the preparation of metallo carbosiloxanes of type Si(OCH2CH2CH2SiMe2[OCH2PPh2M(CO)n])4 (n = 3, M = Ni, 7a; n = 4, M = Fe, 7b; n = 5: M = Mo, 7c; M = W, 7d), Si(OCH2CH2CH2SiMe[OCH2PPh2Ni(CO)3]2)4 (8) and Me2Si(OCH2CH2CH2SiMe[OCH2PPh2Ni(CO)3]2)2 (11) is described. The reaction of Si(OCH2CH2CH2SiMeXCl)4 (1: X = Me, 2: X = Cl) or Me2Si(OCH2CH2CH2SiMeCl2)2 (9) with HOCH2PPh2 (3) produces Si(OCH2CH2CH2SiMe2(OCH2PPh2))4 (4), Si(OCH2CH2CH2SiMe(OCH2PPh2)2)4 (5) or Me2Si(OCH2CH2CH2SiMe(OCH2PPh2)2)2 (10) in presence of DABCO. Treatment of the latter molecules with Ni(CO)4 (6a), Fe2(CO)9 (6b), M(CO)5(Thf) (6c: M = Mo; 6d: M = W), respectively, gives the title compounds 7a-7d, 8 and 11 in which the PPh2 groups are datively bound to a 16-valence-electron metal carbonyl fragment.The formation of analytical pure and uniform branched and dendritic metallo carbosiloxanes is based on elemental analysis, and IR, 1H, 13C{1H}, 29Si{1H} and 31P{1H} NMR spectroscopic studies. In addition, ESI-TOF mass spectrometric studies were carried out. 相似文献
18.
Antonio Antiñolo Rafael Fernández-Galán Antonio Otero Ana M. Rodríguez 《Journal of organometallic chemistry》2009,694(13):1959-3497
The allyl-substituted group 4 metal complexes [M{(R)CH(η5-C5Me4)(η5-C5H4)}Cl2] [M = Ti, R = CH2CHCH2, (2); R = CH2C(CH3)CH2 (3); M = Zr, R = CH2CHCH2 (4), R = CH2C(CH3)CH2 (5)] have been synthesized by the reaction of allyl ansa-magnesocene derivatives and the tetrachloride salts of the corresponding transition metal. The dialkyl complexes ] [M = Ti, R = CH2=CHCH2, R′ = Me (6), R′ = CH2Ph (7); R = CH2C(CH3)CH2, R′ = Me (8), R′ = CH2Ph (9); M = Zr, R = CH2CHCH2, R′ = Me (10), R′ = CH2Ph (11); R = CH2C(CH3)CH2, R′ = Me (12), R′ = CH2Ph (13)] have been synthesized by the reaction of the corresponding ansa-metallocene dichloride complexes 2-5 and two molar equivalents of the alkyl Grignard reagent. Compounds 2-5 reacted with H2 under catalytic conditions (Wilkinson’s catalyst or Pd/C) to give the hydrogenation products [M{(R)CH(η5-C5Me4)(η5-C5H4)}Cl2] [M = Ti and R = CH2CH2CH3 (14) or R = CH2CH(CH3)2 (15); M = Zr and R = CH2CH2CH3 (16) or R = CH2CH(CH3)2 (17)]. The reactivity of 2-5 has also been tested in hydroboration and hydrosilylation reactions. The hydroboration reactions of 3, 4 and 5 with 9-borabicyclo[3.3.1]nonane (9-BBN) yielded the complexes [M{(9-BBN)CH2CH(R)CH2CH(η5-C5Me4)(η5-C5H4)}Cl2] [M = Ti and R = H (18); M = Zr and R = H (19) or R = CH3 (20)]. The reaction with the silane reagents HSiMe2Cl gave the corresponding [M{ClMe2SiCH2CHRCH2CH(η5-C5Me4)(η5-C5H4)}Cl2] [M = Ti and R = H (21); M = Zr and R = H (22) or R = CH3 (23)]. The reaction of 22 with t-BuMe2SiOH produced a new complex [Zr{t-BuMe2SiOSi(Me2)CH2CH2CH2CH(η5-C5Me4)(η5-C5H4)}Cl2] (24) through the formation of Si-O-Si bonds. On the other hand, reactivity studies of some zirconocene complexes were carried out, with the insertion reaction of phenyl isocyanate (PhNCO) into the zirconium-carbon σ-bond of [Zr{(n-Bu)CH(η5-C5Me4)(η5-C5H4)}2Me2] (25) giving [{(n-Bu)CH(η5-C5Me4)(η5-C5H4)]}Zr{Me{κ2-O,N-OC(Me)NPh}] as a mixture of two isomers 26a-b. The reaction of [Zr{(n-Bu)(H)C(η5-C5Me4)(η5-C5H4)}(CH2Ph)2] (27) with CO also provided a mixture of two isomers [{(n-Bu)CH(η5-C5Me4)(η5-C5H4)]}Zr(CH2Ph){κ2-O,C-COCH2Ph}] 28a-b. The molecular structures of 4, 11, 16 and 17 have been determined by single-crystal X-ray diffraction studies. 相似文献
19.
E MeichelTh Stein J KralikG Rheinwald H Lang 《Journal of organometallic chemistry》2002,649(2):191-198
Treatment of [Ti](Cl)(CCSiMe3) (1) {[Ti]=(η5-C5H5)2Ti} with Ni(CO)4 (2) in a 1:1 molar ratio produces the heterobimetallic early-late transition metal complex {[Ti](Cl)(CCSiMe3)}Ni(CO) (3), which features a low-valent Ni(CO) entity stabilized by a datively bonded Cl and a η2-coordinated Me3SiCC ligand. As side-products [Ti]Cl2 (8) and {[Ti](CCSiMe3)2}Ni(CO) (5) are formed. The latter complex can also be synthesized by the reaction of [Ti](CCSiMe3)2 (4) with equimolar amounts of 2. If 3 is reacted with stoichiometric amounts of P(OR)3 (6a, R=C6H5; 6b, R=C6H4CH3-2; 6c, R=C6H4tBu-2) the bis(alkynyl) titanocene 4, (CO)2Ni[P(OR)3]2 (7a, R=C6H5; 7b, R=C6H4CH3-2; 7c, R=C6H4tBu-2), complex 8, {[Ti](μ,η1:η2-CCSiMe3)}2 (9) along with Me3SiCCCCSiMe3 (10) is produced. A possible mechanism for the formation of these species is presented. The solid-state structure of 7b is reported. Complex 7b crystallizes in the tetragonalic space group P-421c with the following parameters: a=14.852(2), b=14.852(2), c=19.410(4) Å, V=4281.5(12) Å3, Z=4 and ρ=1.271 g cm−3. Mononuclear 7b features a Ni(0) centre in a pseudo-tetrahedral environment, caused by the CO and P(OC6H4CH3-2)3 ligands. 相似文献
20.
The complex [(η6-C6Me6)Ru(μ-Cl)Cl]21 react with sodium salts of β-diketonato ligands in methanol to afford the oxygen bonded neutral complexes of the type [(η6-C6Me6)Ru(κ2-O,O′-R1COCHCOR2)Cl] {R1, R2 = CH3 (2), CH3, C6H5 (3), C6H5 (4), OCH3 (5), OC2H5 (6)}. Complex 4 with AgBF4 yields the γ-carbon bonded ruthenium dimeric complex 7. Complex 4 also reacts with tertiary phosphines and bridging ligands to yield complexes of the type [(η6-C6Me6)Ru(κ2-O,O′-C6H5COCHCOC6H5)(L)]+ (L = PPh3 (8), PMe2Ph (9)) and [{η6-C6Me6)Ru(κ2-O,O′-C6H5COCHCOC6H5)}2(μ-L)] L = 4,4′-bipyridine (4,4′-bipy) (11), 1,4-dicyanobenzene (DCB) (12) and pyrazine (Pz) (13). Complexes 2-4 react with sodium azide to yield neutral complexes [(η6-C6Me6)Ru(κ2-O,O′-R1COCHCOR2)N3] {R1, R2 = CH3 (10a), CH3, C6H5 (10b), C6H5 (10c). All these complexes were characterized by FT-IR and FT-NMR spectroscopy as well as analytical data. The molecular structures of complexes [(η6-C6Me6)Ru(κ2-O,O′CH3COCH-COC6H5)Cl] (3) and [(η6-C6Me6)Ru(κ2-O,O′-C6H5COCHCOC6H5] (4) were established by single crystal X-ray diffraction studies. The complex 3 crystallizes in the triclinic space group, [a = 7.9517(4), b = 9.0582(4) and c = 14.2373(8) Å, α = 88.442(3)°, β = 76.6.8(3)° and γ = 81.715(3)°. V = 987.17(9) Å3, Z = 2]. Complex 4 crystallizes in the monoclinic space group, P21/c [a = 7.5894(8), b = 20.708(2) and c = 29.208(3) Å,β = 92.059(3)° V = 4587.5(9) Å3, Z = 8]. 相似文献