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1.
《Journal of Coordination Chemistry》2012,65(2):283-291
Abstract Three dimolybdenum alkyne complexes containing functionally substituted ligands [Mo2(μ-CHCH)(CO)4(η5?C5H4C(O)R)2] [R ? OEt, (1a); R ? Me, (1b); R ? Ph, (1c)] were synthesized by reactions of acetylene with in situ generated metal-metal triply bonded complexes [Mo(CO)2(η5?C5H4C(O)R)]2 (R ? OEt, Me, Ph). Further reaction of (1a), (1b) or (1c) with Co2(CO)8 in refluxing toluene gave another three new butterfly compounds [Co2Mo2-(μ4-CHCH)(μ-CO)4(CO)4(η5-C5H4C(O)R)2] [R ? OEt, (2a); R ? Me, (2b); R ? Ph, (2c)]. The resulting compounds were characterized by elemental analyses, IR, 1H NMR and MS. The crystal structure of (2b) was determined by single-crystal X-ray analysis. The results indicate that the existence of functional groups on the cyclopentadienyl ring has an influence on the reactivity of this type of complex. 相似文献
2.
《Journal of organometallic chemistry》1991,402(3):C56-C58
Complete self-recognition of chirality is observed in the Michael addition of the enolate derived from R,S-[η5-C5H5Fe(CO)(PPh3-COCH3] to the acryloyl complex R,S-[(η5-C5H5Fe(CO)(PPh3)-COCHCH2)] to generate exclusively the single diastereoisomer of the glutaroyl complex RR,SS-[(η5-C5H5)Fe(CO)(PPh3)COCH2]2CH2. 相似文献
3.
Mohamed F. Meidine Catherine J. Meir Stephen Morton John F. Nixon 《Journal of organometallic chemistry》1985,297(2):255-263
Syntheses of the complexes trans-[PtCl2(PR3)Mo2(CO)4(η5-C5H5)2(tBuCP)], (PR3=PEt3, PPr3, PBu3, PPh2Me, PPhMe2) trans-[PdCl2(PBu3)Mo2(CO)4(η5-C5H5)2(tBuCP)], and trans[RhCl{(PF2NMe)2CO}Mo2(CO)4(η5-C5H5)2(tBuCP)] are described and their 31P NMR spectra presented and discussed. 相似文献
4.
鉴于含硅-过渡金属键化合物作为催化剂具有重要的应用价值, 在我们最近发现的化合物(η5,η5-C5H4Me2SiSi-Me2C5H4)Fe2(CO)4 (1)的硅硅键和铁铁键复分解重排反应可以有效地合成含有两个硅铁键的环状化合物[Me2Si-η5-C5H4- Fe(CO)2]2 (2)的基础上, 对该硅铁键环状化合物的三苯基膦取代衍生物[Me2Si-η5-C5H4-Fe(CO)(PPh3)][Me2Si-η5-C5H4Fe(CO)2-n(PPh3)n] (3: n=0, 5: n=1)的合成方法进行了研究. 发现化合物1在三苯基膦存在下的复分解重排反应是合成单三苯基膦取代产物3的最好方法; 而双三苯基膦取代化合物5则可通过光照条件下2与三苯基膦发生羰基取代反应而得到, 产物中含有的顺反异构体可利用制备薄层色谱法分离. 利用X射线衍射法测定了化合物3的分子结构, 考察了三苯基膦配体的存在对分子结构的影响以及三苯基膦与铁形成的配位键的稳定性. 相似文献
5.
The neutral complexes (η5-C5H5NiXL (X = Cl, L = PPh3 (I); L = PCy3 (II); X = Br, L = PPh3 (III); L = PCy3 (IV); X = I, L = PPh3 (V); L = PCy3 (VI)) have been obtained by treating NiX2L2 with thallium cyclopentadienide. The same reaction in the presence of TlBF4 gives cationic derivatives [(η5-C5H5)NiL2]BF4 (L = 2PPh2Me (VII); L = dppe (VIII)), whereas mononuclear complexes containing two different ligands (L2 = PPh3 + PCy3 (IX)) or dinuclear [(η5-C5H5)Ni(PPh3)]2dppe(BF4)2 (X) are obtained from the reaction of III with TlBF4 in the presence of a different ligand. Reduction of cationic complexes with Na/Hg gives very unstable nickel(I) derivatives (η5-C5H5)NiL2, which could not be isolated purely. Similar reduction of neutral complexes under CO gives a mixture of decomposition products containing [(η5-C5H5)Ni(CO)]2 and nickel(o) carbonyls, whereas in the presence of acetylenes, dinuclear [(η5-C5H5)Ni]2(RCCR′) (R = R′ = Ph; R = Ph, R′ = H) are obtained. 相似文献
6.
《Journal of Coordination Chemistry》2012,65(3-4):389-400
Abstract The synthesis and properties of new cationic iron(II) complexes of general formula [(η5-C5H5)FeL(η2-dppa)]A [A=I?, L = CO(1); A = BF4, L = CO(2) CH3CN(4), η1-dppa(5); dppa = NH(PPh2)2] are described. The carbonyl complex [(η5-C5H5)Fe(CO)(η2-dppa)]BF4 is deprotonated to give the neutral complex [(η5-C5H5)Fe(CO){η2-(PPh2)2N}](3). All complexes have been characterized by elemental analysis and IR and NMR spectroscopies. Cyclic voltammetry of complexes 1–5 shows a diverse redox chemistry in acetonitrile solution. While the reduction of 1 and 2 leads to the formation of a dinuclear Fe(I) complex, 4 and 5 form mononuclear species of Fe(I); oxidation of metal centers of 1 and 2 is not observed and in complexes 3 and 4 the metal centers are oxidized at potentials < 1. Complex 5 in acetonitrile solution is transformed into complex 4. 相似文献
7.
Reactions of one or two equiv. of cyclohexyl isocyanide in THF at room temperature with Mo?Mo triply bonded complexes [Mo(CO)2(η5‐C5H4R)]2 (R=COCH3, CO2CH3) gave the isocyanide coordinated Mo? Mo singly bonded complexes with functionally substituted cyclopentadienyl ligands, [Mo(CO)2(η5‐C5H4R)]2(μ‐η2‐CNC6H11) ( 1a , R=COCH3; 1b , R=CO2CH3) and [Mo(CO)2(η5‐C5H4R)(CNC6H11)]2 ( 2a , R=COCH3; 2b , R=CO2CH3), respectively. Complexes 1a , 1b and 2a , 2b could be more conveniently prepared by thermal decarbonylation of Mo? Mo singly bonded complexes [Mo(CO)3(η5‐C5H4R)]2 (R=COCH3, CO2CH3) in toluene at reflux, followed by treatment of the resulting Mo?Mo triply bonded complexes [Mo(CO)2(η5‐C5H4R)]2 (R=COCH3, CO2CH3) in situ with cyclohexyl isocyanide. While 1a , 1b and 2a , 2b were characterized by elemental analysis and spectroscopy, 1b was further characterized by X‐ray crystallography. 相似文献
8.
Junpei Kuwabara 《Journal of organometallic chemistry》2005,690(2):269-275
[(η5-C5H5)ZrCl2(η5-C5H4)CMe2(C5H5)] reacted with Co2(CO)8 to produce a heterodinuclear Zr(IV)-Co(I) complex [(η5-C5H5)ZrCl2(η5-C5H4)CMe2(η5-C5H4)Co(CO)2] (3). Complex 3 underwent oxidative addition of I2 to give [(η5-C5H5)ZrCl2(η5-C5H4)CMe2(η5-C5H4)CoI2(CO)] (4) having Zr(IV) and Co(III) centers. The carbonyl ligand of 4 was easily replaced with P(OMe)3 and PPh3 to afford [(η5-C5H5)ZrCl2(η5-C5H4)CMe2(η5-C5H4)CoI2(L)] (5: L = P(OMe)3, 6: L = PPh3). Structures of 5 and 6 were determined by X-ray crystallography. These Zr-Co heterodinuclear complexes catalyzed polymerization of ethylene and propylene. 相似文献
9.
《Journal of organometallic chemistry》1986,310(1):47-54
Protonation of the closely related salts [N(PPh3)2][W(CC6H4Me-4)(CO)2(η-1,2-C2B9H9R2] (Ia, R = H; Ib, R = Me) affords structurally different products: [N(PPh3)2][W2(μ-H){μ-C2(C6H4Me-4)2}(CO)4(η-1,2-C2B9H11)2] (III) and [W(CC6H4Me-4)(CO)2(η-1,2-C2B9H10Me2)] (V), respectively. Treatment of Ib, with PMe3, gives the ketenyl complex [N(PPh3)2][W(CO)(PMe3){η2-C(C6H4Me-4)C(O)}(η-1,2-C2B9H9Me2)] (VI). Protonation and methylation of the latter yields the alkyne-tungsten compounds [W(CO)(PMe3){η-C2(OR′)(C6H4Me-4)}(η-1,2-C2B9H9Me2)] (IXa, R′ = H; IXb, R′ = Me). 相似文献
10.
It is shown that electrode catalysis of substitution reactions can operate even for systems with rather slow chemical steps and, furthermore, for those which are electrochemically irreversible. A procedure is described for synthesis of Fe(CO)(PPh3)(η5-C5H5)COCH3 from Fe(CO)2(η5-C5H5)CH3 and triphenylphosphine. A simplified mechanism for the catalytic chain, is given and discussed in terms of the structure of the reacting species. 相似文献
11.
《Journal of organometallic chemistry》1986,302(3):371-377
Reaction of [WI(CO)2(η7-C7H7)] with dppm (dppm = Ph2PCH2PPh2) or dppe (dppe = Ph2PCH2CH2PPh2) gives the trihaptocycloheptatrienyl complexes [WI(CO)2(L-L)(η3-C7H7)] [L-L = dppm, (A1); L-L = dppe (A2)]. The complex A1 reacts with NH4PF6 to give the unidentate biphosphine complex [W(CO)2(dppm-P)(η7-C7H7)][PF6] (B) which yields [W(CO)(dppm)(η7-C7H7)][PF6] (C) on reaction with Me3NO·2H2O. Substitution of a carbonyl ligand in [W(CO)3(η7-C7H7)][PF6] with the organometallic phosphine ligand [Mo(CO)2(dppe-P)(η7-C7H7)][PF6] yields the heterobimetallic [{W(CO)2(η7-C7H7)}(μ-dppe){Mo(CO)2(η7-C7H7)}x][PF6]2 (D). 相似文献
12.
Brian J. Brisdon Michael Cartwright Annabelle G. Hodson 《Journal of organometallic chemistry》1984,277(1):85-90
Dissolution of [MoCl(CO)2(η3-C3H4R)(NCMe)2] (R = H or Me) in methanol yields yellow conducting solutions containing the [Mo(CO)2(η3-C3H4R)(HOMe)3]+ cations. The same species are formed on dissolution of [Mo(CO)2(η3-C3H4R)(NCMe)3]BF4 in methanol, and one of the cations (R = Me) has been isolated as its tetrafluoroborate salt. There is strong spectroscopic evidence that hydrated allyldicarbonylmolybdenum(II) cations [Mo(CO)2(η3-C3H4R)(H2O)x]+ are present on dissolution of [MoCl(CO)2(η3-C3H4R)(NCMe)2] in deoxygenated water, and treatment of these solutions with bi- and tridentate ligands yields neutral complexes [MoCl(CO)2(η3-C3H4R)L2] (R = H or Me; L2 = 2,2′-bipyridine (bipy) or 2,2′-bipyridylamine (bpa)), and cationic species [Mo(CO)2(η3-C3H4R)L3]+ (R = H or Me; L3 = diethylenetriamine (dien) or bis(2-pyridylmethyl)amine (bpma)) respectively. The latter were isolated as their hexafluorophosphate salts. Addition of Ph4AsCl to basic methanolic solutions of [MoCl(CO)2(η3-C3H4R)(NCMe)2] causes the precipitation of the anionic molybdenum derivatives Ph4As[Mo2(CO)4(η3-C3H4R)2(μ-OMe)3] (R = H or Me). 相似文献
13.
Ph2P(O)C(S)N(H)R (R Me, Ph) reacts with M(CO)3(η5-C5H5)Cl (M Mo, W) in the presence of Et3N to give M(CO)2(η5-C5H5)(Ph2P(O)C(S)NR). The deprotonated ligand coordinates in a bidentate manner through N and S to give a four-membered ring system. M(CO)3(PPh3)2Cl2 (M Mo, W) reacts with Ph2P(O)C(S)N(H)R (R Me, Ph) in the presence of Et3N to give complexes in which the central metal atoms are seven coordinate through two ligands bonded via O and S to form five-membered ring systems, one PPh3, and two CO groups. The complexes were characterised by elemental analyses, IR, 1H NMR, and 31P NMR spectroscopy, and an X-ray structural analysis of Mo(CO)2(PPh3)(Ph2P(O)C(S)NPh)2 · CH2Cl2. 相似文献
14.
《Journal of organometallic chemistry》1987,319(3):311-326
Dehydrogenating complexation of borolenes with carbonyls (Ru3(CO)12, Os3(CO)12), Wilkinson's catalyst (RhCl(PPh3)3) and related compounds (RuCl2(PPh3)3, RuHCl(PPh3)3, OSCl2(PPh3)3), and (η6-arene)ruthenium complexes (Ru(η-C6H6)(η4-C6H8), [Ru(η-C6H6)Cl2]2, [Ru(η-C6-Me6)Cl2]2) leads to the (η5-borole)metal complexes of Ru, Os, and Rh. Inter alia, the preparation of the complexes Ru(CO)3(η5-C4H4BF) (R = Ph, OMe, Me), Os(CO)3L (L = η5-C4H4BPh), MHClL(PPh3)2 (M = Ru, Os), RhClL(PPh3)2, and RuL(η-C6R6) (R = H, Me) is described. The structures of RuHClL(PPh3)2 and RhClL(PPh3)2 have been determined by X-ray diffraction analysis. 相似文献
15.
The complex (η5-C5H4CH3)Mn(NO)(PPh3)I has been prepared by the reaction of NaI with [(η5-C5H4CH3)Mn(NO)(CO)(PPh3)]+ and also by the reaction of [(η5-C5H4CH3)Mn(NO)(CO)2]+ with NaI followed by PPh3. This iodide compound reacts with NaCN to yield (η5-C5H4CH3)Mn(NO)(PPh3)CN which is ethylated by [(C2H5)3O]BF4 to yield [(η5-C5H4CH3)Mn(NO)(PPh3)(CNC2H5)]+. Both [(η5-C5H4CH3)Mn(NO)(CO)2]+ and [(η5-C5H4CH3)Mn(NO)(PPh3)(CO)]+ react with NaCN to yield [(η5-C5H4CH3)Mn(NO)(CN)2]?. This anion reacts with Ph3SnCl to yield cis-(η5-C5H4CH3)Mn(NO)(CN)2SnPh3 and with [(C2-H5)3O]BF4 to yield [(η5-C5H4CH3)Mn(NO)(CNC2H5)2]+. The reaction of (η5-C5-H4CH3)Mn(NO)(PPh3)I with AgBF4 in acetonitrile yields [(η5-C5H4CH3)Mn-(NO)(PPh3)(NCCH3)]+. The complex (η5-C5H4CH3)Mn(NO)(CO)I, produced in the reaction of [(η5-C5H4CH3)Mn(NO)(CO)2]+ with NaI, is not stable and decomposes to the dimeric complex (η5-C5H4CH3)2Mn2(NO)3I for which a reasonable structure is proposed. Similar dimers can be prepared from the other halide salts. The reaction of (η7-C7H7)Mo(CO)(PPh3)I with NaCN yields (η7-C7-H7)Mo(CO)(PPh3)CN which is ethylated by [(C2H5)3O]BF4 to yield [(η7-C7H7)-Mo(CO)(PPh3)(CNC2H5)]+. The interaction of this molybdenum halide complex with AgBF4 in acetonitrile and pyridine yields [(η7-C7H7)Mo(CO)(PPh3)-(NCCH3)]+ and [(η7-C7H7)Mo(CO)(PPh3)(NC5H5)]+, respectively. Both (η5-C5-H4CH3)Mn(NO)(PPh3)I and (η7-C7H7)Mo(CO)(PPh3)I are oxidized by NOPF6 to the respective 17-electron cations in acetonitrile at ?78°C but revert to the neutral halide complex at room temperature. This result is supported by electrochemical data. 相似文献
16.
Michel O. Albers Neil J. Coville Eric Singleton 《Journal of organometallic chemistry》1982,232(3):261-266
The reaction between Fe(CO)5, and group V donor ligands L, (L PPh3, AsPh3, SbPh3, PMePh2, PMe2Ph, Asme2Ph, P(C6H11)3, P(n-Bu)3, P(i-Bu)3, P(OPh)3, P(OEt)3, P(OMe)3) in the presence of [(η5-C5Me5Fe(CO)2]2 (R H, Me) or [(η5-C5Me5)Fe(CO)2]2 as catalyst in refluxing toluene, rapidly gives the complexes Fe(CO)4L in yields > 85%. The reaction rate is essentially independent of the nature of L for [(η5-C5Me5)Fe(CO)2]2 as catalyst. For the other catalysts, the rate is influenced predominantly by the steric properties of L. These results are interpreted in terms of the interaction between the catalyst and the ligand L to give derivatives of the type (η5-C5H4R)2Fe2,(CO)3,(L). These derivatives were also found to catalyse the reaction between Fe(CO)5, and L. The complexes [(η-C5H4R)Fe(CO)2]2 (R H, Me) and [(η5-C5Me5)Fe(CO)2]2 also catalyse the reaction between Mn2(CO)10 and PPh3 to give Mn2(CO)8- PPh3)2 in > 80% yield. 相似文献
17.
The enolate derived from [(η5-C5H5)Fe(PPh3)(CO)(COCH3)] and n-butyl lithium reacts stereoselectively with imines to yield β-amino-acyl complexes which on oxidationv give β-lactams. 相似文献
18.
Richard H. Hooker Antony J. Rest Ian Whitwell 《Journal of organometallic chemistry》1984,266(2):c27-c30
Infrared spectroscopic experiments using polyvinyl chloride film matrices at 12–200 K have shown for the first time that the photoinduced decarbonylation of Fe(η5-C5H5)(CO)2(COCH3) is thermally reversible, and that the photolysis of Fe(η5-C5H5)(CO)2(CH3) leads to the reversible formation of the new species Fe(η5-C5H5)(CO)(CH3). 相似文献
19.
[MoCl(CO)3(η5-C5H5)] on photolysis with allyl or crotyl halides C5H4RX gives MoIV complexes [MoX2(CO)(η3-C3H4R)(η5-C5H5)] (R = H, X = Cl, Br, I; R = Me, X = Cl, Br). [WCl(CO)3(η5-C5H5)] under similar conditions gives trihalides [WX3(CO)2(η5-C5H5)] (X = Cl, Br) on reaction with C3H5Cl and C3H5Br while [WCl(CO)3(η5-C5H4SiMe3)] and [CrI(CO)3(η5-C5H5)] react with allyl chloride to give [WCl3(CO)2(η5-C5H4SiMe3)] and [CrCl2(η5-C5H5)] respectively. 相似文献
20.
《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