共查询到20条相似文献,搜索用时 31 毫秒
1.
Xu-Feng Liu 《Journal of Coordination Chemistry》2017,70(1):116-126
Four diiron dithiolate complexes with monophosphine ligands have been prepared and structurally characterized. Reactions of (μ-SCH2CH2S-μ)Fe2(CO)6 or [μ-SCH(CH3)CH(CH3)S-μ]Fe2(CO)6 with tris(4-chlorophenyl)phosphine or diphenyl-2-pyridylphosphine in the presence of Me3NO·2H2O afforded diiron pentacarbonyl complexes with monophosphine ligands (μ-SCH2CH2S-μ)Fe2(CO)5[P(4-C6H4Cl)3] (1), (μ-SCH2CH2S-μ)Fe2(CO)5[Ph2P(2-C5H4N)] (2), [μ-SCH(CH3)CH(CH3)S-μ]Fe2(CO)5[P(4-C6H4Cl)3] (3), and [μ-SCH(CH3)CH(CH3)S-μ]Fe2(CO)5[Ph2P(2-C5H4N)] (4) in good yields. Complexes 1–4 were characterized by elemental analysis, 1H NMR, 31P{1H} NMR and 13C{1H} NMR spectroscopy. Furthermore, the molecular structures of 1–4 were confirmed by X-ray crystallography. 相似文献
2.
Xu-Feng Liu 《Journal of Coordination Chemistry》2016,69(17):2620-2629
Four diiron toluenedithiolate complexes 2–5 with monophosphine ligands are reported. Treatment of [μ-SC6H3(CH3)S-μ]Fe2(CO)6 (1) with tris(3-chlorophenyl)phosphine, tris(4-chlorophenyl)phosphine, tris(4-methylphenyl)phosphine or 2-(diphenylphosphino)benzaldehyde, and Me3NO?2H2O in MeCN resulted in the formation of [μ-SC6H3(CH3)S-μ]Fe2(CO)5[P(3-C6H4Cl)3] (2), [μ-SC6H3(CH3)S-μ]Fe2(CO)5[P(4-C6H4Cl)3] (3), [μ-SC6H3(CH3)S-μ]Fe2(CO)5[P(4-C6H4CH3)3] (4), and [μ-SC6H3(CH3)S-μ]Fe2(CO)5[Ph2P(2-C6H4CHO)] (5) in 64–82% yields. Complexes 2–5 have been characterized by elemental analysis, IR, 1H NMR, 31P{1H} NMR, 13C{1H} NMR and further confirmed by single crystal X-ray diffraction analysis. The molecular structures show that 2–5 contain a butterfly diiron toluenedithiolate cluster coordinated by five terminal carbonyls and an apical monophosphine. 相似文献
3.
《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
4.
Jiří Pinkas Ivana Císařová Róbert Gyepes Jiří Kubišta Karel Mach Michal Horáček 《Transition Metal Chemistry》2016,41(2):143-152
Bis{(diphenylvinylsilyl)tetramethylcyclopentadienyl}titanium dichloride [TiCl2{η5-C5Me4(SiPh2CH=CH2)}2] (1) is reduced with a half molar equivalent of magnesium to the monochloride ([TiCl{η5-C5Me4(SiPh2CH=CH2)}2] (2), whereas one molar equivalent of magnesium affords the titanocene [Ti{η5-C5Me4(SiPh2CH=CH2)}{η5:η2-C5Me4(SiPh2CH=CH2)}] (3) stabilized by η2-coordination of one of the two vinyl groups to titanium(II). In the presence of excess magnesium, the vinyl moieties of 3 undergo intramolecular coupling to afford the ansa-titanocene [Ti(η5:η5:η2-C5Me4SiPh2CH=CHCH2CH2SiPh2C5Me4)] (4) possessing the η2-coordinated double bond in lateral position of its ansa-chain. The symmetrical ansa-titanocene [Ti(η5:η5:η2-C5Me4SiPh2CH2CH=CHCH2SiPh2C5Me4)] (5) was not obtained although its DFT-calculated energy is only slightly higher than that of 4. It is considered that transient 5 gives rise to non-identified tar-like by-products which inherently accompany the formation of 4. 相似文献
5.
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
6.
《Journal of Coordination Chemistry》2012,65(3-4):379-388
Abstract The UV irradiation of (η5-C5Me5)Re(CO)3 in the presence of 1,2,4,5-C6Cl4H2 and 1,3,5-C6Cl3H3 (λ = 350 nm, hexane solution) effected intramolecular C—Cl activation, generating the complexes trans-(η5-C5Me5)Re(CO)2(2,4,5-C6Cl5-nHn)Cl, ((1), n = 2; (2), n = 3), respectively. Complex (1) dissolved in polar organic solvents produces, an equilibrium mixture with its cis isomer. The reaction of (1) with AgBF4, in acetonitrile, led to formation of the cationic complex [cis-(η5-C5Me5)Re(CO)2(2,4,5-C6Cl3H2)(MeCN)]+. The tetramethylfulvene complex (η6-C5Me4CH2)Re(CO)2(2,4,5-C6Cl3H2) (3) was obtained by reacting the cationic complex with the fluorinating agent Et3N′3HF. 相似文献
7.
Ji?í Pinkas Ana Conde Michal Horá?ek Karel Mach 《Journal of organometallic chemistry》2009,694(13):1971-2586
Elimination of methane during thermolysis of title compounds results in the formation of σ-Ti-C bond to t-butyl or benzyl group. The t-butyl-containing titanocene methyl compound [Ti(III)Me(η5-C5Me4t-Bu)2] (5) eliminates methane at 110 °C to give cleanly [Ti(III)(η5:η1-C5Me4CMe2CH2)(η5-C5Me4t-Bu)] (6). The methyl derivative of analogous benzyl-containing titanocene [Ti(III)Me(η5-C5Me4CH2Ph)2] was not isolated because it eliminated methane at ambient temperature to give [Ti(III)(η5:η1-C5Me4CH2-o-C6H4)(η5-C5Me4CH2Ph)] (7) with one phenyl ring linked to titanium atom in ortho-position. The corresponding titanocene dimethyl compound [TiMe2{η5-C5Me4t-Bu)}2] (9) eliminates two methane molecules at 110 °C to give the singly tucked-in 1,1-dimethylethane-1,2-diyl-tethered titanocene [Ti{η5:η1:η1-C5Me3(CH2)(CMe2CH2)}(η5-C5Me4t-Bu)] (11). In distinction, the analogous benzyl derivative [TiMe2(η5-C5Me4CH2Ph)2] (10) eliminates at 110 °C only one methane molecule to afford [TiMe(η5:η1-C5Me4CH2-o-C6H4)(η5-C5Me4CH2Ph)] (12) containing one phenyl group attached to titanium in o-position and one methyl group persisting on the titanium atom. This compound is stable at 150 °C for at least 3 h. The crystal structures of 5, 6, 7, and 10 were determined. 相似文献
8.
Julia Hitzbleck 《Journal of organometallic chemistry》2007,692(21):4702-4707
Half-sandwich dibenzyl complexes of scandium have been prepared by stepwise treatment of scandium trichloride with lithium derivatives of silyl-functionalized tetramethylcyclopentadienes (C5Me4H)SiMe2R (R = Me, Ph) and benzyl magnesium chloride. The resulting complexes [Sc(η5-C5Me4SiMe3)(CH2Ph)2(THF)] and [Sc(η5-C5Me4SiMe2Ph)(CH2Ph)2(1,4-dioxane)] show structure related to that of the corresponding bis(trimethylsilylmethyl) compounds [Sc(η5-C5Me4SiMe2R)(CH2SiMe3)2(THF)]. The four-coordinate complexes display η1-coordinated benzyl ligands without significant interaction of the ipso-carbon of the phenyl moiety. Conversion of [Sc(η5-C5Me4SiMe3)(CH2Ph)2(THF)] into the cationic species by treatment with triphenylborane in THF led to the formation of a stable charge separated complex [Sc(η5-C5Me4SiMe3)(CH2Ph)(THF)x][BPh3(CH2Ph)]. Benzyl cation formed using [Ph3C][B(C6F5)4] in toluene resulted in a moderately active syndiospecific styrene polymerization catalyst. 相似文献
9.
Venugopal Shanmugham Sridevi 《Journal of organometallic chemistry》2007,692(22):4909-4916
The reaction of [Ru3(CO)12] (1), with indene in refluxing xylene affords [{(η5-C9H7)Ru(CO)2}2] (2), in high yield. An analogous reaction of 1 with 2-phenylindene affords the expected dinuclear complex [{(η5-C9H6Ph)Ru(CO)2}2] (5), and a heptaruthenium cluster [(C9H4Ph)Ru7(μ-H)(μ-CO)2(CO)16] (6). The indenyl ligand in compound 6 exhibits a novel bonding mode in which the benzenoid ring is μ4,η1:η1:η2:η2 bound to the cluster. Refluxing 1 with bis-indenyl methane affords the dinuclear complex [Ru2(CO)4{μ-(η5-C9H6)2CH2}] (7), which reacts with iodine via Ru-Ru bond cleavage to give [Ru2I2(CO)4{(η5-C9H6)2CH2}] (8). 相似文献
10.
《Journal of Coordination Chemistry》2012,65(15):2517-2530
AbstractThe reactions of the starting complex, [Fe2(CO)6{μ-SCH2CH (CH2CH3)S}] (1), with the phosphine ligands tris(4-methylphenyl)phosphine, diphenyl-2-pyridylphosphine, tris(4-fluorophenyl)phosphine, 2-(diphenylphosphino)benzaldehyde, or benzyldiphenylphosphine in the presence of the decarbonylating agent Me3NO·2H2O yielded the corresponding phosphine-substituted diiron butane-1,2-dithiolate complexes [Fe2(CO)5(L){μ-SCH2CH(CH2CH3)S}] (L?=?P(4-C6H4CH3)3, 2; Ph2P(2-C5H4N), 3; P(4-C6H4F)3, 4; Ph2P(2-C6H4CHO), 5; Ph2PCH2Ph, 6) in 75%–87% yields. The complexes have been characterized by elemental analysis, IR, 1H, and 31P{1H} NMR spectroscopy, as well as by single-crystal X-ray diffraction analysis. Moreover, the electrochemistry of 2–4 was studied by cyclic voltammetry, suggesting that they can catalyze the reduction of protons to H2 in the presence of HOAc. 相似文献
11.
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
12.
《Polyhedron》1987,6(12):2067-2071
Reactions between diphenyl(vinyl)phosphine and the compounds [FeW(μ-CC6H4Me-4)(CO)5(η5-C5Me5)] and [FeMo(μ-CC6H4Me-4)(CO)6(η5-C5H5)] result in a coupling of the vinyl and p-tolylmethylidyne groups at the dimetal centres to produce the PPh2 · CH · CH2 · C(C6H4Me-4) fragment, which bridges the metal-metal bonds. This was confirmed by an X-ray diffraction study on [FeW{μ-PPh2 · CH · CH2 · C(C6H4Me-4)}(CO)5(η5-C5Me5)]. 相似文献
13.
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
14.
Synthesis, Structure, and Reactivity of the Ferrioarsaalkene [(η5‐C5Me5)(CO)2FeAs=C(Ph)NMe2] Reaction of equimolar amounts of the carbenium iodide [Me2N(Ph)CSMe]I and LiAs(SiMe3)2 · 1.5 THF afforded the thermolabile arsaalkene Me3SiAs = C(Ph)NMe2 ( 1 ), which in situ was converted into the black crystalline ferrioarsaalkene [(η5‐C5Me5)(CO)2FeAs=C(Ph)NMe2)] ( 2 ) by treatment with [(η5‐C5Me5)(CO)2FeCl]. Compound 2 was protonated by ethereal HBF4 to yield [(η5‐C5Me5)(CO)2FeAs(H)C(Ph)NMe2]BF4 ( 3 ) and methylated by CF3SO3Me to give [(η5‐C5Me5)(CO)2FeAs(Me)C(Ph)NMe2]‐ SO3CF3 ( 4 ). [(η5‐C5Me5)(CO)2FeAs[M(CO)n]C(Ph)NMe2] ( 5 : [M(CO)n] = [Fe(CO)4]; 6 : [Cr(CO)5]) were isolated from the reaction of 2 with [Fe2(CO)9] or [{(Z)‐cyclooctene}Cr(CO)5], respectively. Compounds 2 – 6 were characterized by means of elemental analyses and spectroscopy (IR, 1H, 13C{1H}‐NMR). The molecular structure of 2 was determined by X‐ray diffraction analysis. 相似文献
15.
Zhihong Ma Xinli Zhang Hong Wang Zhangang Han Xuezhong Zheng 《Journal of Coordination Chemistry》2017,70(4):709-721
The complexes [(η5-C9H6R)Re(CO)3] [R = nBu (8), tBu (9), CH(CH2)4 (10), Ph (11), Bz (12), 4-methoxyphenyl (13), 4-chlorophenyl (14)] were synthesized by refluxing substituted indenyl ligands [C9H7R] [R = nBu (1), tBu (2), CH(CH2)4 (3), Ph (4), Bz (5), 4-methoxyphenyl (6), 4-chlorophenyl (7)], and Re2(CO)10 in decalin. The molecular structures of 9, 10, 12, and 13 were determined by X-ray diffraction analysis. These four crystals have similar molecular structures of the mononuclear carbonyl complex. In each of these molecules, Re is η5-coordinated to the five-membered ring of the indenyl group. Complexes 8–14 have catalytic activity for Friedel-Crafts reactions of aromatic compounds with a variety of alkylation and acylation reagents. Compared with traditional catalysts, these mononuclear metal carbonyl complexes have obvious advantages such as high activities, mild reaction conditions, high selectivity, and environmentally friendly chemistry. 相似文献
16.
Nevin Arslan 《Phosphorus, sulfur, and silicon and the related elements》2020,195(8):628-637
AbstractThe interaction of [Ru(η6-arene)(μ-Cl)Cl]2 and Ir(η5-C5Me5)(μ-Cl)Cl]2 with a new Ionic Liquid-based phosphinite ligand, [(Ph2PO)-C6H9N2Ph]Cl, (2) gave [Ru((Ph2PO)-C6H9N2Ph)(η6-p-cymene)Cl2]Cl (3), [Ru((Ph2PO)-C6H9N2Ph)(benzene)Cl2]Cl (4) and [Ir((Ph2PO)-C6H9N2Ph)(C5Me5)Cl2]Cl (5), complexes. All the compounds were characterized by a combination of multinuclear NMR and IR spectroscopy as well as elemental analysis. Furthermore, the Ru(II) and Ir(III) catalysts were applied to asymmetric transfer hydrogenation of acetophenone derivatives using 2-propanol as a hydrogen source. The results showed that the corresponding alcohols could be obtained with good activity (up to 55% ee and 99% conversion) under mild conditions. Notably, [Ir((Ph2PO)-C6H9N2Ph)(C5Me5)Cl2]Cl (5) is more active than the other analogous complexes in the transfer hydrogenation (up to 81% ee). 相似文献
17.
A series of metal-containing vinylic monomers of the type LnM(COC6H4CH=CH2) and LnM (COCH=CHC6H5) [LnM = (η5-C5H5)Fe(CO)2, (η5-C5Me5)Fe(CO)2 and (η5-C5H5)W(CO)3] were prepared by the reaction of the appropriate metal anion with either 4-vinylbenzoyl chloride or cinnamoyl chloride. (η5-C5H5)(CO)2FeCOCH=CH2 was prepared by the reaction of Na[(η5-C5H5)Fe(CO)2] and acryloyl chloride, whereas the compound (η5-C5H5)(CO)2Fe(C6H4CH=CH2) was prepared via a transmetallation reaction using a palladium catalyst. All compounds were fully characterized using FTIR, 1H and 13C NMR spectroscopy and mass spectrometry. Copyright © 1998 John Wiley & Sons, Ltd. 相似文献
18.
The reaction of complex [μ-SCH(CH3)CH(CH3)S-μ]Fe2(CO)6 (1) with trans-1,2-bis(diphenylphosphino)ethylene (trans-dppv) in the presence of Me3NO?2H2O in CH2Cl2/CH3CN afforded complex {[μ-SCH(CH3)CH(CH3)S-μ]Fe2(CO)5}2(trans-dppv) (2) with a bridging dppv. Complex [μ-SCH(CH3)CH(CH3)S-μ]Fe2(CO)4(cis-dppv) (3) was prepared by the reaction of 1 with cis-dppv and Me3NO?2H2O. The new complexes 2 and 3 were characterized by elemental analysis, spectroscopy, and X-ray diffraction analysis. 相似文献
19.
《Journal of Coordination Chemistry》2012,65(5):407-415
The complexes [MI2(CO)3(NCMe)2] (M=Mo or W) react in CH2Cl2 at room temperature with two equivalents of 4,4'-diphenylenecarbonitrile (dpc) to afford the new seven-coordinate complexes, [MI2(CO)3(4,4'-dpc-N)2] (1 and 2) in good yield. Equimolar quantities of [MI2(CO)3(NCMe)2] and PPh3 give [MI2(CO)3(NCMe)(PPh3)], which react in situ with 4,4'-dpc to yield the mono-4,4'-diphenylenecarbonitrile complexes, [MI2(CO)3(4,4'-dpc-N)(PPh3)] (3 and 4). Treatment of the bis(alkyne) complexes, [WI2(CO)(NCMe)(η 2-RC2R)2] (R=Me and Ph) with one equivalent of 4,4'-dpc in CH2Cl2 at room temperature affords the acetonitrile displaced products, [WI2(CO)(4,4'-dpc-N)(η 2-RC2R)2] (5 and 6). Reaction of equimolar quantities of [WI2(CO)(NCMe)(η 2-PhC2Ph)2] and 2 in CH2Cl2 at room temperature gives the 4,4'-dpc-bridged complex, [WI2(CO){WI2(CO)3(4,4'-dpc-N)(4,4'-dpc- N,N')}(η 2-PhC2Ph)2] (7) in good yield. Similarly, equimolar amounts of [WI2(CO)(NCMe)(η 2-RC2R)2] (R=Me and Ph) and (4) react in CH2Cl2 to afford the bimetallic complexes, [WI2(CO){WI2(CO)(4,4'-dpc-N,N')(PPh3)}(η 2-RC2R)2] (8 and 9). The new bimetallic 4,4'-dpc-bridged alkyne complexes, [WI2(CO){WI2(CO)(4,4'-dpc-N,N')(η 2-MeC2Me)2}(η 2-MeC2Me)2] [(10), [WI2(CO){WI2(CO)(4,4'-dpc-N,N')(η 2-PhC2Ph)2}(η 2-PhC2Ph)2] (11) and [WI2(CO){WI2(CO)(4,4'-dpc-N,N')(η 2-MeC2Me)2}(η 2-PhC2Ph)2] (12) are also described. 相似文献
20.
《Journal of organometallic chemistry》1988,346(1):C4-C6
Reaction-solution calorimetric studies involving the complexes Ti[η5-C5(CH3)5]2-(CH3)2, Ti[η5-C5(CH3)5]2(CH3), Ti[η5-C5(CH3)5]2(C6H5), Ti[η5-C5(CH3)5]2Cl2, and Ti[η5-C5(CH3)5]2Cl, have enabled derivation of titaniumcarbon and titaniumchlorine stepwise bond dissociation enthalpies in these species. 相似文献