共查询到20条相似文献,搜索用时 31 毫秒
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Michael I. Bruce Benjamin G. Ellis Allan H. White 《Journal of organometallic chemistry》2005,690(3):792-801
Whereas {Ru(dppm)Cp*}2(μ-CCCC) (2) is the only product formed by deprotonation of [{Ru(dppm)Cp*}2{μ(CCHCHC)}]+ with dbu, a mixture of 2 with Ru{CCCHCH(PPh2)2[RuCp*]}(dppm)Cp* (3) and {Cp*Ru(PPh2CHCCH-)}2 (4) is obtained with KOBut. A similar reaction with [{Ru(dppm)Cp*}2{μ(CCMeCMeC)}]+ (5) gave Ru{CCCMeCH(PPh2)2[RuCp*]}(dppm)Cp* (6). X-ray structures of 4, 5 and 6 confirm the presence of the 1-ruthena-2,4-diphosphabicyclo[1.1.1]pentane moiety, which is likely formed by an intramolecular attack of the deprotonated dppm ligand on C(1) of the vinylidene ligand. Protonation of {Ru(dppe)Cp*}2(μ-CCCC) (8-Ru) regenerates its precursor [{Ru(dppe)Cp*}2{μ(CCHCHC)}]2+ (7-Ru). Ready oxidation of the bis(vinylidene) complex affords the cationic carbonyl [Ru(CO)(dppe)Cp*]PF6 (9) (X-ray structure). 相似文献
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The alkenylaminoallenylidene complex [Ru(η5-C9H7){CCC(NEt2)[C(Me)CPh2]}{κ(P)-Ph2PCH2CHCH2}(PPh3)][PF6] (2) has been prepared by the reaction of the allenylidene [Ru(η5-C9H7)(CCCPh2){κ(P)-Ph2PCH2CHCH2}(PPh3)][PF6] (1) with the ynamine MeCCNEt2. The reaction proceeds regio- and stereoselectively, and the insertion of the ynamine takes place exclusively at the CβCγ bond of the unsaturated chain. The secondary allenylidene [Ru(η5-C9H7){CCC(H)[C(Me)CPh2]}{κ(P)-Ph2PCH2CHCH2}(PPh3)][PF6] (3) is obtained, in a one-pot synthesis, from the reaction of aminoallenylidene 2 with LiBHEt3 and subsequent treatment with silica. Moreover, the addition of an excess of NaBH4 to a solution of the complex 2 in THF at room temperature gives exclusively the alkynyl complex [Ru(η5-C9H7){CCCH2[C(Me)CPh2]}{κ(P)-Ph2PCH2CHCH2}(PPh3)] (5). The heating of a solution of allenylidene derivative 3 in THF at reflux gives regio- and diastereoselectively the cyclobutylidene complex [Ru(η5-C9H7) (PPh3)][PF6](4) through an intramolecular cycloaddition of the CC allyl and the CαCβ bonds in the allenylidene complex 3. The structure of complex 4 has been determined by single crystal X-ray diffraction analysis. 相似文献
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The new ferrole Fe2(CO)6[μ-η2,η4-(Fc)CC{C(H)C(R)S}CC(SiMe3)] [R = SiMe3 (1) and R = Fc (2)] and ruthenoles Ru2(CO)6[μ-η2,η4-(Me3Si)CC{SC(Fc)C(H)}CC(Fc)] 3 and Ru2(CO)6[μ-η2,η4-(Me3Si)CC(SCCFc)C(H)C(Fc)] 4, have been obtained from the reactions of M3(CO)12 (M = Fe, Ru) and FcCCSCCSiMe3 through S-C bond activations and C-C coupling reactions. Thermolysis of Ru2(CO)6[μ3-η2,η4,η3-(Me3Si)CC{SC(Fc)C(SCCSiMe3}Ru(CO)3}CC(Fc)] alone and in the presence of HCCFc, yielded the compounds Ru2(CO)6[μ-η2,η4-(Me3Si)CC{SC(Fc)C(SCCSiMe3)}CC(Fc)] 5 and Ru2(CO)6[μ-η2,η4-(Me3Si)CC{SC(Fc)C(SCCSiMe3)C(H)C(Fc)}CC(Fc)] 6, respectively. The crystal structures of the compounds 1, 3, 4 and 6 are reported. 相似文献
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The synthesis of the new ruthenium(II) allenylidene complex [ClRu(dppe)2CCC11H6N2][OTf] (4) (dppe = 1,2-bis(diphenylphosphino)ethane) terminated with a 4,5-diazafluorene ligand is reported. Further coordination of that metal allenylidene to ruthenium and rhenium moieties leads to the bimetallic adducts [ClRu(dppe)2CCC11H6N2{Ru(bpy)2}][B(C6F5)4]3 (5a), [ClRu(dppe)2CCC11H6N2{Ru(tBu-bpy)2}][PF6]3 (5b) and [ClRu(dppe)2CCC11H6N2{Re(CO)3Cl}][OTf] (6). Their optical and electrochemical properties show that the allenylidene moiety is an attractive molecular clip for the access to larger original redox-active homo/heteronuclear multi-component supramolecular assemblies. The X-ray crystal structure of the allenylidene metal building block is also described. 相似文献
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Kamil I. Utegenov 《Journal of organometallic chemistry》2011,696(21):3408-3414
The addition of phosphines to the manganese allenylidene complexes Cp(CO)2MnCCC(Ph)R (R = H, Ph) proceeds selectively at the Cα atom to result in the α-phosphonioallenyl complexes Cp(CO)2Mn−-C(+PR31)CC(Ph)R. The protonation of the latter affords the η2-(1,2)-phosphonioallenes Cp(CO)2Mn{η2-(1,2)-HC(+PR31)CC(Ph)R}, rather than the phosphoniovinylcarbenes Cp(CO)2MnC(+PR31)-HCC(Ph)R. All complexes obtained are stereochemically rigid and do not isomerize into the η2-(2,3)-phosphonioallene isomers. 相似文献
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Victorio Cadierno 《Journal of organometallic chemistry》2005,690(8):2087-2096
The novel bis(iminophosphorano)methanes CH2[P{NP(S)(OR)2}Ph2]2 (R = Ph (1a), Et (1b)) have been obtained by oxydation of dppm with the corresponding thiophosphorylated azides (RO)2P(S)N3. Deprotonation of 1a,b with KH generates the methanide species KCH[P{NP(S)(OR)2}Ph2]2 (R = Ph (2a), Et (2b)). The ruthenium(II) dimer [{Ru(η6-p-cymene)(μ-Cl)Cl}2] reacts with 2a,b to afford the cationic complexes [Ru(η6-p-cymene)(κ3-C,N,S-CH[P{NP(S)(OR)2}Ph2]2)]+ (R = Ph (3a), Et (3b)), via selective κ3-C,N,S-coordination of the bis(iminophosphorano)methanide anions to ruthenium. The structure of [Ru(η6-p-cymene)(κ3-C,N,S-CH[P{NP(S)(OEt)2}Ph2]2)][PF6] (3b) has been confirmed by single-crystal X-ray crystallography. Deprotonation of complexes 3a,b with NaH leads to the neutral carbene derivatives [Ru(η6-p-cymene)(κ2-C,N-C[P{NP(S)(OR)2}Ph2]2)] (R = Ph (4a), Et (4b)). 相似文献
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Selby A.R. Knox 《Journal of organometallic chemistry》2007,692(19):4119-4128
The diruthenium μ-allenyl complex [Ru2(CO)(NCMe)(μ-CO){μ-η1:η2-C(H)CC(Me)(Ph)}(Cp)2][BF4], 3b, reacts with halide anions to yield the neutral derivatives [Ru2(CO)2(X){μ-η1:η2-C(H)CC(Me)(Ph)}(Cp)2] [X = Cl, 4b; X = Br, 4c; X = I, 4d]. Complex 4b undergoes isomerization to the unprecedented bridging vinyl-chlorocarbene species [Ru2(CO)(μ-CO){μ-η1:η3- C(Cl)C(H)C(Me)(Ph)}(Cp)2], 10, upon filtration of a CH2Cl2 solution through an alumina column.Complex 3b reacts with an excess of NaBH4 to give five products: the allene complex [Ru2(CO)2{μ-η2:η2- CH2CC(Me)(Ph)}(Cp)2], 5; the hydride species trans-[Ru2(CO)2(μ-H){μ-η1:η2-CHCC(Me)(Ph)}(Cp)2], 6, and cis-[Ru2(CO)2(μ-H){μ-η1:η2-CHCC(Me)(Ph)}(Cp)2], 8; the vinyl-alkylidene [Ru2(CO)(μ-CO){μ-η1:η3- C(H)C(H)C(Me)(Ph)}(Cp)2], 9; and the cluster [Ru3(CO)3(μ-H)3(Cp)3], 7.Studies on the thermal stabilities of 5, 6, 8 and 9 have suggested a plausible mechanism for the formation of these complexes and for the synthesis of 10. 相似文献
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Michael I. Bruce Benjamin G. Ellis Allan H. White 《Journal of organometallic chemistry》2005,690(7):1772-1783
Several complexes have been obtained from reactions carried out in early attempts to prepare the diynyl complexes Ru(CCCCR)(dppe)Cp* (R = H, SiMe3). These have been identified crystallographically as the acyl complex Ru{CCC(O)Me}(dppe)Cp* (3), the cationic imido complex [Ru{CCC(NH2)Me}(dppe)Cp*]PF6 (4), the binuclear butenynylallenylidene [{Ru(dppe)Cp*}2{μ-CCC(OMe)CHCMeCC}]PF6 (5), and the bis(ethynyl)cyclobutenylidene [{Ru(dppe)Cp*}2{μ-CCC4H2(SiMe3)CC}]PF6 (6). NMR studies of 5 have revealed the existence of two isomers. Plausible routes for their formation from the putative butatrienylidene intermediate [Ru(CCCCH2)(dppe)Cp*]+ (A) are discussed. 相似文献
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Michael I. Bruce Martyn Jevric Allan H. White 《Journal of organometallic chemistry》2011,696(2):461-467
In contrast to the simple diynyl complexes formed in reactions between HCCCCFc and MCl(dppe)Cp∗; (M = Fe, Ru), an analogous reaction with RuCl(PPh3)2Cp∗; in the presence of KPF6 and dbu resulted in dimerisation of the diyne at the Ru centre to afford a mixture of [Ru{η1,η2-C(CCFc)C(L)CHCCCHFc}(PPh3)Cp∗]PF6 (L = dbu 1, PPh32). Similar reactions with RuCl(PR3)2L gave [Ru{η1,η2-C(CCFc)C(dbu)CHCCCHFc}(PR3)L]PF6 (L = Cp, R = Ph 3, m-tol 4; L = η5-C9H7, R = Ph 5). The reaction between 3 and I2, followed by crystallization of the paramagnetic product from MeOH, afforded the dicationic [Ru{C(CCFc)C(dbu)CHC(OMe)C(OMe)CHFc}(PPh3)Cp](I3)26. The molecular structures of 2·2CH2Cl2 and 6.S (S = 2CH2Cl2, C6H6) were determined by single-crystal XRD studies. 相似文献