共查询到20条相似文献,搜索用时 15 毫秒
1.
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
2.
《Journal of organometallic chemistry》2002,641(1-2):62-66
The intense purple colored bi- and trimetallic complexes {Ti}(CH2SiMe3)[CC(η6-C6H5)Cr(CO)3] (3) ({Ti}=(η5-C5H5)2Ti) and [Ti][CC(η6-C6H5)Cr(CO)3]2 (5) {[Ti]=(η5-C5H4SiMe3)2Ti}, in which next to a Ti(IV) center a Cr(0) atom is present, are accessible by the reaction of Li[CC(η6-C6H5)Cr(CO)3] (2) with {Ti}(CH2SiMe3)Cl (1) or [Ti]Cl2 (4) in a 1:1 or 2:1 molar ratio. The chemical and electrochemical properties of 3, 5, {Ti}(CH2SiMe3)(CCFc) [Fc=(η5-C5H5)Fe(η5-C5H4)] and [Ti][(CC)nMc][(CC)mM′c] [n, m=1, 2; n=m; n≠m; Mc=(η5-C5H5)Fe(η5-C5H4); M′c=(η5-C5H5)Ru(η5-C5H4); Mc=M′c; Mc≠M′c] will be comparatively discussed. 相似文献
3.
Reaction of C5H4(SiMe3)2 with Mo(CO)6 yielded [(η5-C5H3(SiMe3)2)Mo(CO)3]2, which on addition of iodine gave [(η5-C5H3(SiMe3)2Mo(CO)3I]. Carbonyl displacement by a range of ligands: [L P(OMe)3, P(OPri)3,P(O-o-tol)3, PMe3, PMe2Ph, PMePh2, PPh3, P(m-tol)3] gave the new complexes [(η5-C5H3(SiMe3)2 MO(CO)2(L)I]. For all the trans isomer was the dominant, if not exclusive, isomer formed in the reaction. An NOE spectral analysis of [(η5-C5H3(SiMe3)2)Mo(CO)2(L)I] L PMe2Ph, P(OMe)3] revealed that the L group resided on the sterically uncongested side of the cyclopentadienyl ligand and that the ligand did not access the congested side of the molecule. Quantification of this phenomenon [L P(OMe)3] was achieved by means of the vertex angle of overlap methodology. This methodology revealed a steric preference with the trans isomer (less congestion of CO than I with an SiMe3 group) being the more stable isomer for L P(OMe)3. 相似文献
4.
The compounds (η5-C5R5)2Fe2(CO)2(μ-CO)(μ-CH2) (R = H, CH3) have been prepared through the reaction of chloromethyl pivalate with the appropriate metal anions, η5-C5H5Fe(CO)2K and η5-C5Me5Fe(CO)2K. 相似文献
5.
The interaction of [(η5-C5H4But)2YbCl · LiCl] with one equivalent of Li[(CH2) (CH2)PPh2] in tetrahydrofuran gave [Ph2PMe2][(η5-C5H4But)2Li] (1) and [(η5-C5H4But)2Yb(Cl)CH2P(Me)Ph2] (2) in 10% and 30% yields, respectively. 1 could also be prepared in 70% yield from the reaction of [Ph2PMe2][CF3SO3] with two equivalents of (C5H4But)Li. Both compounds have been fully characterized by analytical, spectroscopic and X-ray diffraction methods. The solid state structure of 1 reveals a sandwich structure for the [(η5-C5H4But)2Li]− anion. 相似文献
6.
《Journal of organometallic chemistry》2004,689(11):1919-1929
Reduction of methyl-substituted titanocene dichlorides bearing pendant double bonds [TiCl2{η5-C5Me4(CH2CMeCH2)}2] (1) and [TiCl2{η5-C5Me4(SiMe2(CH2)2CHCH2)}2] (2) with magnesium yielded diamagnetic Ti(IV) compound [Ti{η1:η1:η5-C5Me3(CH2)(CH2CH(Me)CH2)}{η5-C5Me4(CH2C(Me)CH2)}] (4) and paramagnetic Ti(III) compound [Ti{η5-C5Me4(SiMe2CH2CHCHMe)}(μ-η3,η1:η5,η1(Ti:Mg){C5Me3(CH2)(SiMe2CHCHCMe)})Mg(OC4H8)2] (6), respectively. The reluctance of titanocene intermediates to undergo intramolecular cyclization to cyclopentadienyl-ring-tethered titanacycles (as typically observed) can be explained by a shortness of the 2-methylallyl group and steric hindrance of its double bond in the former case and, in the latter case, by an attack of magnesium on the titanocene intermediate, faster than cyclization reactions. The crystal structures of 4 and 6 were determined by single-crystal X-ray diffraction. 相似文献
7.
Mark B. Fischer Donald F. Gaines Jeffrey A. Ulman 《Journal of organometallic chemistry》1982,231(1):55-62
Reaction of 2-XB5H8 (X Cl, Br) with Naco(CO)4 produces the transiently stable 2-[Co(CO)4]B5H8. The similar 2-[(η5-C5H5)Fe(CO)2]B5H8, which exhibits much greater thermal stability, is prepared by reaction of LiB5H8 with (η5-C5H5)Fe(CO)2I. Reactions of CO2(CO)8 with B5H9 under a variety of conditions produce 2-[Co(CO)4]B5H8 along with an inseparable impurity that appears to be 1-[Co(CO)4]B5H8. 相似文献
8.
Dmitry A. Loginov 《Journal of organometallic chemistry》2009,694(2):157-12442
Complex Cp∗PtCl2 (Cp∗ = η-C4Me4) reacts with the carborane anions [7,8-C2B9H11]2− and [9-SMe2-7,8-C2B9H10]− giving platinacarboranes Cp∗Pt(η-7,8-C2B9H11) (1) and [Cp∗Pt(η-9-SMe2-7,8-C2B9H10)]+ (2), respectively. Reactions of the [Cp∗Pt]2+ fragment (as a labile nitromethane solvate) with the sandwich compounds Cp∗Fe(η-C5H3Me2BMe) and Cp∗Rh(η5-C4H4BPh) afford the triple-decker cations [Cp∗Pt(μ-η:η-C5H3Me2BMe)FeCp∗]2+ (3) and [Cp∗Pt(μ-η5:η5-C4H4BPh)RhCp∗]2+ (4) with bridging boratabenzene and borole ligands. The structures of 1 and 3(CF3SO3)2 were determined by X-ray diffraction. 相似文献
9.
Jan Honzí?ek Abhik Mukhopadhyay Carlos C. Romão 《Journal of organometallic chemistry》2010,695(5):680-2319
The synthesis of new cyclopenta[l]phenanthrenyl complexes [(η5-C17H10Me)(η3-C3H5)Mo(CO)2] and [(η5-C17H9(COOMe)N(CH2)4)(η3-C3H5)Mo(CO)2] is described. Although these compounds are structural analogues their reactivity is different. Protonation of [(η5-C17H10Me)(η3-C3H5)Mo(CO)2] gives a stable ionic compound [(η5-C17H10Me)Mo(CO)2(NCMe)2][BF4] while its analogue containing both tertiary amino and carboxylic ester groups [(η5-C17H9(COOMe)N(CH2)4)(η3-C3H5)Mo(CO)2] decomposes under the same conditions. [(η5-C17H10Me)Mo(CO)2(NCMe)2][BF4] reacts with cyclopentadiene to give a stable η4-complex [(η4-C5H6)(η5-C17H10Me)Mo(CO)2][BF4] that was successfully oxidized to the Mo(IV) dicationic compound [(η5-C5H5)(η5-C17H10Me)Mo(CO)2][Br][BF4]. 相似文献
10.
The iridium and rhodium complexes [MCl(CO)2(NH2C6H4Me-4)] (M = Ir or Rh) react with [Os3(μ-H)2(CO)10] to give the tetranuclear clusters [MOs3(μ-H)2(μ-Cl)(CO)12]; the iridium compound being structurally identified by X-ray diffraction. Similarly, [IrCl(CO)2(NH2C6H4Me-4)] and [Rh2(μ-CO)2(η-C5Me5)2] afford the tetranuclear cluster [Ir2Rh2(μ-CO)(μ3-CO)2(CO)4(η-C5Me5)2], also characterised by single-crystal X-ray crystallog 相似文献
11.
Two silyl-zirconium compounds (η-C5H5)2ZrCl[Si(CH3)3] (I) and (η-C5H5)2-Zr[Si(CH3)3]2 (II), have been prepared by the reaction of (η-C5H5)2ZrCl2 with Hg[Si(CH3)3]2 in refluxing benzene. While I is unreactive toward 1-hexyne (55–60°C) and CO (350 psi), the zirconiumsilicon bond is cleaved by electrophiles such as Cl2, HgCl2, and AlCl3. 相似文献
12.
Luigi Busetto M. Cristina Cassani Vincenzo G. Albano 《Journal of organometallic chemistry》2005,690(3):818-824
The new dianionic ligand [Na]2[C5H4CO2(CH2)2NTs] (1) having an alkoxycarbonyl and an amide group in the same side chain has been prepared by a single step, high yield procedure. The synthesis of the related rhodium complexes [Rh{η5-C5H4CO2(CH2)2N(H)Ts}(NBD)] (3) and [Rh{η5-C5H4CO2 (CH2)2N(Me)Ts}(NBD)] (4) is reported as well as their X-ray molecular structures. 相似文献
13.
Roy Buschbeck 《Journal of organometallic chemistry》2005,690(5):1198-1204
The synthesis of titanocenedichloride end-grafted carbosiloxane dendrimers of the 1st and 2nd generation is reported. To find the optimal reaction conditions, Me2ClSiH (1) was reacted with (η5-C5H4SiMe2CHCH2)(η5-C5H5)TiCl2 (2). The best result could be obtained with the Karstedt catalyst, whereby exclusively the β-isomer ((η5-C5H4SiMe2CH2CH2SiMe2Cl)(η5-C5H5)TiCl2, 3) is formed. Under similar conditions Me3SiOCH(Me)(CH2)4SiMe2H (4) reacts with 2 to give (η5-C5H4SiMe2CH2CH2SiMe2(CH2)4CH-(Me)OSiMe3)(η5-C5H5)TiCl2 (5). When using MeSi(OCH(Me)(CH2)4SiMe2H)3 (6), Si(OCH(Me)(CH2)4SiMe2H)4 (8) and MeSi[O(CH2)3SiMe(OCH(Me)(CH2)4SiMe2H)2]3 (10) instead of 1 and 4, the respective metallo dendrimers MeSi[OCH(Me)(CH2)4-SiMe2CH2CH2SiMe2(η5-C5H4)(η5-C5H5)TiCl2]3 (7), Si[OCH(Me)(CH2)4SiMe2CH2CH2SiMe2(η5-C5H4)(η5-C5H5)TiCl2]4 (9) and MeSi{O(CH2)3SiMe[OCH(Me)(CH2)4SiMe2CH2CH2SiMe2(η5- C5H4)(η5-C5H5)TiCl2]2}3 (11) can be isolated.Compounds 3, 5, 7, 9 and 11 were characterised by elemental analysis as well as IR and NMR spectroscopy (1H, 13C{1H}, 29Si{1H}). 相似文献
14.
Experimental evidence that the dinuclear complex Me2Si[η5-C5H4Fe(CO)2-(η1-CH2C6H5)]2 shows enhanced reactivity over its mononuclear analogy η5-C5H5Fe(CO)2(η1-CH2C6H5 in photogragmentation to produce bibenzyl and FeFe bonded product is presented. Information from a series of competition and crossover experiments indicate that two factors are involved in the enhancement: (1) the ability to photochemically produce a 16-electron unsaturated benzyl unit in close proximity to a saturated partner, and (2) the inability of the FeFe bonded species 4 to quench free benzyl radicals in solution. Chemical reaction of Me2Si[η5-C5H4Fe(CO)2(η1-CH2C6H5)]2 with Me3NO produces bibenzyl and establishes that loss of CO is the initial step in the fragmentation reaction. In addition, trapping experiments with 9,10-dihydroanthracene show that bibenzyl is formed from free benzyl radical; BBased on these results an overall mechanism is proposed. 相似文献
15.
《Journal of organometallic chemistry》2001,634(2):109-121
The reaction of the dilithium salt Li2[Me2Si(C5H4)(C5Me4)] (2) of Me2Si(C5H5)(C5HMe4) (1) with [MCl(C8H12)]2 (M=Rh, Ir) and [RhCl(CO)2]2 afforded homodinuclear metal complexes [{Me2Si(η5-C5H4)(η5-C5Me4)}{M(C8H12)}2] (M=Rh: 3; M=Ir: 4) and [{Me2Si(η5-C5H4)(η5-C5Me4)}Rh2(CO)2(μ-CO)] (5), respectively. The reaction of 2 with RhCl(CO)(PPh3)2 afforded a mononuclear metal complex [{Me2Si(C5HMe4)(η5-C5H4)}Rh(CO)PPh3] (6) leaving the C5HMe4 moiety intact. Taking advantage of the difference in reactivity of the two cyclopentadienyl moieties of 2, heterodinuclear complexes were prepared in one pot. Thus, the reaction of 2 with RhCl(CO)(PPh3)2, followed by the treatment with [MCl(C8H12)]2 (M=Rh, Ir) afforded a homodinuclear metal complex [Rh(CO)PPh3{(η5-C5H4)SiMe2(η5-C5Me4)}Rh(C8H12)] (7) consisting of two rhodium centers with different ligands and a heterodinuclear metal complex [Rh(CO)(PPh3){(η5-C5H4)SiMe2(η5-C5Me4)}Ir(C8H12)] (8). The successive treatment of 2 with [IrCl(C8H12)]2 and [RhCl(C8H12)]2 provided heterodinuclear metal complex [Ir(C8H12){(η5-C5H4)SiMe2(η5-C5Me4)}Rh(C8H12)] (9). The reaction of 2 with CoCl(PPh3)3 and then with PhCCPh gave a mononuclear cobaltacyclopentadiene complex [{Me2Si(C5Me4H)(η5-C5H4)}Co(CPhCPhCPhCPh)(PPh3)] (10). However, successive treatment of 2 with CoCl(PPh3)3, PhCCPh and [MCl(C8H12)]2 in this order afforded heterodinuclear metal complexes [M(C8H12){(η5-C5H4)SiMe2(η5-C5Me4)}Co(η4-C4Ph4)] (M=Rh: 11; M=Ir: 12) in which the cobalt center was connected to the C5Me4 moiety. Although the heating of 10 afforded a tetraphenylcyclobutadiene complex [{Me2Si(C5Me4H)(η5-C5H4)}Co(η4-C4Ph4)] (13), in which the cobalt center was connected to the C5H4 moiety, simple heating of the reaction mixture of 2, CoCl(PPh3)3 and PhCCPh resulted in the formation of a tetraphenylcyclobutadiene complex [{Me2Si(C5H5)(η5-C5Me4)}Co(η4-C4Ph4)] (14), in which the cobalt center was connected to the C5Me4 moiety. The mechanism of the cobalt transfer was suggested based on the electrophilicity of the formal trivalent cobaltacyclopentadiene moiety. In the presence of 1,5-cyclooctadiene, the reaction of 2 with CoCl(PPh3)3 provided a mononuclear cobalt cyclooctadiene complex [{Me2Si(C5Me4H)(η5-C5H4)}Co(C8H12)] (15). The reaction of 15 with n-BuLi followed by the treatment with [MCl(C8H12)]2 (M=Rh, Ir) afforded the heterodinuclear metal complexes of [Co(C8H12){(η5-C5H4)SiMe2(η5-C5Me4)}M(C8H12)] (M=Rh: 16; M=Ir: 17). Treatment of 6 with Fe2(CO)9 at room temperature afforded a heterodinuclear metal complex [{Me2Si(C5HMe4)(η5-C5H4)}{Rh(PPh3)(μ-CO)2Fe(CO)3}] (18) in which the C5HMe4 moiety was kept intact. Treatment of dinuclear metal complex 5 with Fe2(CO)9 afforded a heterotrinuclear metal complex [{(η5-C5H4)SiMe2(η5-C5Me4)}{Rh(CO)Rh(μ-CO)2Fe(CO)3}] (19) having a triangular metal framework. The crystal and molecular structures of 3, 11, 12, 18 and 19 have been determined by single-crystal X-ray diffraction analysis. 相似文献
16.
《Journal of organometallic chemistry》2002,649(1):21-24
The complexes [(η5-C5H5)Fe(CO)2(SCCR)] (R=tBu, SiMe3) have been obtained by reaction of [(η5-C5H5)Fe(CO)2I] and the corresponding LiSCCR. These are the first examples of mononuclear iron compounds containing alkynethiolate ligands. The crystal structure of [(η5-C5H5)Fe(CO)2(SCCSiMe3)] has been determined by X-ray diffraction. The role of [(η5-C5H5)Fe(CO)2(SCCSiMe3)] as a metalloligand in its reactions with metal carbonyls has been explored. 相似文献
17.
Alexander Hildebrandt 《Journal of organometallic chemistry》2011,696(20):3231-3237
The synthesis and properties of heterobimetallic Ti-M complexes of type {[[Ti](μ-η1:η2-CCSiMe3)][M(μ-η1:η2-CCSiMe3)(CO)4]} (M = Mo: 5, [Ti] = (η5-C5H5)2Ti; 6, [Ti] = (η5-C5H4SiMe3)2Ti; M = W: 7, [Ti] = (η5-C5H5)2Ti; 8, [Ti] = (η5-C5H4SiMe3)2Ti) and {[Ti](μ-η1:η2-CCSiMe3)2}MO2 (M = Mo: 13, [Ti] = (η5-C5H5)2Ti; 14, [Ti] = (η5-C5H4SiMe3)2Ti). M = W: 15, [Ti] = (η5-C5H5)2Ti; 16, [Ti] = (η5-C5H4SiMe3)2Ti) are reported. Compounds 5-8 were accessible by treatment of [Ti](CCSiMe3)2 (1, [Ti] = (η5-C5H5)2Ti; 2, [Ti] = (η5-C5H4SiMe3)2Ti) with [M(CO)5(thf)] (3, M = Mo; 4, M = W) or [M(CO)4(nbd)] (9, M = Mo; 10, M = W; nbd = bicyclo[2.2.1]hepta-2,5-diene), while 13-16 could be obtained either by the subsequent reaction of 1 and 2 with [M(CO)3(MeCN)3] (11, M = Mo; 12, M = W) and oxygen, or directly by oxidation of 5-8 with air. A mechanism for the formation of 5-8 is postulated based on the in-situ generation of [Ti](CCSiMe3)((η2-CCSiMe3)M(CO)5), {[Ti](μ-η1:η2-CCSiMe3)2}-M(CO)4, and [Ti](μ-η1:η2-CCSiMe3)((μ-CCSiMe3)M(CO)4) as a result of the chelating effect exerted by the bis(alkynyl) titanocene fragment and the steric constraints imposed by the M(CO)4 entity.The molecular structure of 5 in the solid state were determined by single crystal X-ray diffraction analysis. In doubly alkynyl-bridged 5 the alkynides are bridging the metals Ti and Mo as a σ-donor to one metal and as a π-donor to the other with the [Ti](CCSiMe3)2Mo core being planar. 相似文献
18.
Henri Brunner Gundelinde Kerkien Joachim Wachter 《Journal of organometallic chemistry》1982,224(3):295-300
η5-C5H5(CO)2FeNa reacts with the benzimide chlorides C6H5(Cl)CNR (R CH(CH3)2, C6H5) in boiling THF to give the η1-iminoacyl complexes η5-C5H5 (CO)2Fe[η1-C(C6H5)NR]. Alternatively, the new Fe complexes [η5-C5H5(CO)FeCH3PF6 (IV) and [η5-C5H5(CO)2FeC(C6H5)N(CH3)C(C6H5)NCH3]PF6 (V) are formed under the same conditions, if R CH3. Hudrolysis of the CN single bond of the ligand in V, not stabilized by a chelate effects as in IV, results in the formation of [η5-C5H5(CO)2FeC(C6H5)NHCH3]PF6 (VII). Reaction of η5-C5H5(CO)2 with N-benyzylbenzimido chloride yields η5-C5H5(CO)2FeCH2C6H5 as the only isolated product. 相似文献
19.
Reactions of ligands 2-vinylpyridine 1, 4-vinylpyridine 2, 2-allylpyridine 3, 1-allylpyrazole 4, acrylonitrile 5 and allylcyanide 6 with the metallocene derivatives [Mo(η5-C5H5)2H3][PF6] 7, [Mo(η5-C5H5)2HI] 8, [W(η5-C5H5)2H3] [PF6] 9, [Mo(η5-C5H5)2H2] 10, [M(η5-C5H5)2Br2], M = Mo 11, M = W 12 are described. Reaction of 7 with 1, 8 with 1, 3 with 8 and 4 with 8 gave mixtures of metallocyle isomers resulting from coordination of the nitrogen atom to molybdenum followed by internal hydrometallation; reaction of 11 with 1 gave an olefinic π complex; reaction of either 9 or 11 with 1 gave intractable oils; reactions of 8 with 2, 11 with 5, 12 with 5, 11 with 6 and 12 with 6 yielded monosubstituted products in which the ligand is N-coordinated. 相似文献
20.
On the Reactivity of (η5-C5Me5)(CO)2FeP(SiMe3)2 Toward P-Chloromethylene phosphanes The reaction of (η5-C5Me5)(CO)2FeP(SiMe3)2 ( 2 ) with three equivalents of Cl? P?C(SiMe3)2 ( 3a ) afforded the 3-methanediyl-1,3,5,6-tetraphosphabicyclo[3.1.0]hex-2-ene (η5-C5Me5)(CO)2Fe? ( 6a ). In contrast, 2 reacts with two equivalents of Cl? P?C(Ph)SiMe3 ( 3b ) to give the thermolabile (η5-C5Me5) · (CO)2Fe? P[P?C(Ph)SiMe3]2 ( 4b ) which decomposed during the reaction with further 3b. 4 b was also obtained from (η5-C5Me5)(CO)2Fe? P(SiMe3)? P?C(SiMe3)2 ( 1a ) and two equivalents of 3b . 相似文献