共查询到20条相似文献,搜索用时 31 毫秒
1.
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
2.
Sascha Dietrich 《Journal of organometallic chemistry》2011,696(3):739-747
The synthesis and characterization of novel amidoamine-based metallodendrimers with heterobimetallic end-grafted amidoferrocenyl-palladium-allyl chloride units is described. Dendrimer (Fe((η5-C5H4PPh2)(η5-C5H4))C(O)HNCH2CH2NHC(O)CH2CH2)N[CH2CH2N(CH2CH2C(O)NHCH2CH2NH-C(O)(Fe(η5-C5H4)(η5-C5H4PPh2)))2]2 (9-Fe) and the corresponding metal species (Fe((η5-C5H4PPh2(Pd(η3-C3H5)Cl))(η5-C5H4))C(O)HNCH2CH2NHC(O)CH2CH2)N[CH2CH2N(CH2CH2C(O)NHCH2CH2NHC(O)(Fe(η5-C5H4)(η5-C5H4PPh2(Pd(η3-C3H5)Cl))))2]2 (9-Fe-Pd) were prepared by a consecutive divergent synthesis methodology including addition-amidation cycles, standard peptide coupling, and coordination procedures. For comparative reasons also the monomeric and dimeric molecules (Fe(η5-C5H4PPh2)(η5-C5H4C(O)NHnC3H7)) (5-Fe) and [Fe(η5-C5H4PPh2)(η5-C5H4C(O)NHCH2)]2 (6-Fe) as well as N(CH2CH2C(O)NHCH2CH2NHC(O)(Fe(η5-C5H4)(η5-C5H4PPh2)))3 (7-Fe) and [CH2N(CH2CH2C(O)NHCH2CH2NHC(O)(Fe(η5-C5H4)(η5-C5H4PPh2)))2]2 (8-Fe) were prepared from Fe(η5-C5H4PPh2)(η5-C5H4CO2H) (3). Using [Pd(η3-C3H5)Cl]2 (4) as palladium source heterobimetallic metallodendrimers (Fe(η5-C5H4PPh2(Pd(η3-C3H5)Cl))(η5-C5H4C(O)NHnC3H7)) (5-Fe-Pd), [Fe(η5-C5H4PPh2(Pd(η3-C3H5)Cl))(η5-C5H4C(O)NHCH2)]2 (6-Fe-Pd), N(CH2CH2C(O)NHCH2CH2NHC(O)(Fe(η5-C5H4)(η5-C5H4PPh2(Pd(η3-C3H5)Cl))))3 (7-Fe-Pd) and [CH2N(CH2CH2C(O)NHCH2CH2NHC(O)(Fe(η5-C5H4)(η5-C5H4PPh2(Pd(η3-C3H5)Cl))))2]2 (8-Fe-Pd) were synthesized. Additionally, seleno-phosphines of 5-Fe-Se and 9-Fe-Se, respectively, were prepared by addition of elemental selenium to 5-Fe or 9-Fe to estimate their σ-donor properties.The palladium-containing amidoamine supports are catalytically active in the Heck-Mizoroki cross-coupling of iodobenzene with tert-butyl acrylate. The catalytic data are compared to those obtained for the appropriate mononuclear and dinuclear compounds 5-Fe-Pd and 6-Fe-Pd. This comparison confirms a positive cooperative effect. The mercury drop test showed that (nano)particles were formed during catalysis, following on heterogeneous carbon-carbon cross-coupling. 相似文献
3.
Eight ionic organotin compounds [R2SnCl2(2-quin)]−(HNEt3)+ have been synthesized by reactions of 2-quinH with R2SnCl2 (R = PhCH21, 2-Cl-C6H4CH22, 4-Cl-C6H4CH23, 2-F-C6H4CH24, 4-F-C6H4CH25, 4-CN-C6H4CH26, Ph 7, 2,4-Cl2-C6H3CH28) in the presence of organic base NEt3, and their structures have been characterized by elemental analysis, IR and multinuclear NMR (1H, 13C, 119Sn) spectroscopies. The structure of [(2,4-Cl2-C6H3CH2)2SnCl2(2-quin)]−(NEt3)+ (8) has been determined by X-ray diffraction study. Studies show that compound 8 has a monomeric structure with the central tin atom six-coordinate in a distorted octahedral configuration and the nitrogen atoms of the 2-quin ligands are coordinating to the tin atom in all the eight compounds. 相似文献
4.
Román Andrés Ernesto de Jesús F. Javier de la Mata Juan C. Flores Rafael Gómez 《Journal of organometallic chemistry》2005,690(4):939-943
The cyclopentadienyl(β-diketiminato)titanium and zirconium chlorides (η5-C5H5)MCl2(CH(C(NC6H4-4-OR)CH3)2) (M = Ti (4-dend), Zr (5-dend)), where R corresponds to the first generation carbosilane dendron (dendritic wedge) Si(CH2CH2SiMePh2)3, have been synthesised. After activation with methylaluminoxane, the activity of 4-dend and 5-dend as catalysts for ethylene polymerisation has been determined and compared with that of the non-dedritic counterpart (η5-C5H5)MCl2(CH(C(NC6H5)CH3)2) (M = Ti (4), Zr (5)). 相似文献
5.
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
6.
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
7.
The new mononuclear palladium(II) and platinum(II) [M(p-SC6F4(CF3))2(dppe)] complexes M = Pd 1a, Pt 2a; [M(o-SC6H4(CF3))2(dppe)] M = Pd 1d, Pt 2d as well as the previously known [M(SC6F5)2(dppe)] M = Pd 1b, Pt 2b and [M(p-SC6HF4)2(dppe)] M = Pd 1c, Pt 2c, have been used as metalloligands for the preparation of the heteroleptic bimetallic complexes [M2(μ-SRf)2(dppe)2](SO3CF3)2 M = Pd, Rf = p-C6F4(CF3) 3a, C6F53b, p-C6HF43c, o-C6H4(CF3) 3d; M = Pt, Rf = p-C6F4(CF3) 4a, C6F54b, p-C6HF44c and o-C6H4(CF3) 4d. Variable temperature 19F NMR experiments show that the fluorothiolate bridged bimetallic compounds are fluxional in solution whereas mononuclear complexes are not. The solid state X-ray diffraction structures of [Pd(p-SC6HF4)2(dppe)] (1c), [Pt(SC6F5)2(dppe)] (2b) and [Pt(o-SC6H4(CF3))2(dppe)] (2d) show square-planar coordination around the metal centers. The solid state molecular structure of the compound [Pt2(μ-o-SC6H4(CF3))2(dppe)2](SO3CF3)2 (4d), exhibit a planar [Pt2(μ-S)2] ring with the sulfur substituents in an anti configuration. 相似文献
8.
Three highly fluorinated bipyridine derivatives (4,4′-bis(RfCH2OCH2)-2,2′-bpy) {Rf=HCF2(CF2)7 (1a), n-C8F17 (1b), n-C10F21 (1c)} have been synthesized using 4,4′-bis(BrCH2)-2,2′-bpy and the corresponding fluorinated alkoxides. The fluorine contents of ligands 1a-c are 58.3, 59.8, and 62.3%, respectively. Despite its high fluorine content, the ligand 1a with a -CF2H polar terminal group is more soluble in organic solvents. The ligand 1b is a white solid and is still moderately soluble in CH2Cl2. The ligand 1c has a high fluorophilicity, the partition ratio being 42:1 for the n-C8F18/CH2Cl2 system. The reaction of ligands 1a-c with [PdCl2(CH3CN)2] results in the novel Pd complexes [PdCl2(4,4′-bis-(RfCH2OCH2)-2,2′-bpy)] where Rf=HCF2(CF2)7 (2a), n-C8F17 (2b), n-C10F21 (2c), respectively. The Pd complex 2b is a pale yellow solid, and has been tested unsatisfactorily for FBC. Insoluble in organic solvents, the Pd complex 2c dissolves only in fluorinated solvents, for instance FC77, which is mainly n-C8F18. The novel Pd complex 2c has been tested as a catalyst in Heck reactions under a fluorous biphasic catalysis condition. It was found that the Pd complex 2c, after an easy separation, keeps its catalytic activity (>90% yield), even after seven runs. The TGA studies indicate that the Pd complexes 2a-c are stable up to 330 °C. 相似文献
9.
Xiu-Feng Hou 《Journal of organometallic chemistry》2004,689(13):2228-2235
Sulfur and oxygen functionalized cyclopentandienyl half-sandwich cobalt dicarbonyl complexes [η5-C5H4(CH2)2SCH2CH3]Co(CO)2 (3) and [η5-C5H4(CH2)2OCH3]Co(CO)2 (7) were prepared. Oxidation of 3 or 7 with I2 led to formation of 18-electron complexes [η5-C5H4(CH2)2SCH2CH3]CoI2 (4) and [η5-C5H4(CH2)2OCH3]Co(CO)I2 (8). The reactions of diiodide complex (4) with dilithium 1,2-dicarba-closo-dodecaborane(12)-1,2-dichalcogenolates [(THF)3LiE2C2B10H10Li(THF)]2 [E=S (1a), Se (1b)] afforded 18-electron mononuclear complexes [η5-C5H4(CH2)2SCH2CH3]Co(E2C2B10H10) [E=S (5a), Se (5b)] in which sulfur atoms of side-chain were attached via an intramolecular coordination. Complex 7 reacted with 1a and 1b to give the binuclear complexes {[η5-C5H4(CH2)2OCH3]Co(E2C2B10H10)}2 [E=S (10a), Se (10b)]. The molecular structures of 5a and 10b were determined by X-ray crystallographic analysis. According to the X-ray structure analyses, 10b contains two o-carborane diselenolate bridges, and each Cp′Co fragment is attached to one terminal and two bridging selenolato ligands. The central Co2Se2 four-membered ring is planar, and the direct metal-metal interaction is absent. 相似文献
10.
The reaction of [Pt2Me4(μ-SMe2)2] with ligands 4-C6H5C6H4CHNCH2CH2NMe2 (1a) and 2-C6H5C6H4CHNCH2CH2NMe2 (1b) carried out in acetone at room temperature produced compounds [PtMe2{4-C6H5C6H4CHNCH2CH2NMe2}] (2a) and [PtMe2{2-C6H5C6H4CHNCH2CH2NMe2}] (2b), respectively, in which the imines act as bidentate [N,N′] ligands. Cyclometallated [C,N,N′] compounds [PtMe{4-C6H5C6H3CHNCH2CH2NMe2}] (3a) and [PtMe{2-C6H5C6H3CHNCH2CH2NMe2}] (3b), were obtained by refluxing toluene solutions of compounds 2a or 2b. Reaction of [Pt2Me4(μ-SMe2)2] with ligands 4-C6H5C6H4CHNCH2Ph (1c) and 2-C6H5C6H4CHNCH2Ph (1d) produced compounds [PtMe{4-C6H5C6H3CHNCH2Ph}SMe2] (5c) and [PtMe{2-C6H5C6H3CHNCH2Ph}SMe2] (5d) containing a [C,N] ligand, from which triphenylphosphine derivatives 6c and 6d were also prepared. In all cases, metallation took place to yield five-membered endo-metallacycles and formation of seven-membered or of exo-metallacycles was not observed. The reactions of 3a, 3b, 6c and 6d with methyl iodide were studied in acetone and gave the corresponding cyclometallated platinum (IV) compounds. All compounds were characterised by NMR spectroscopy and compounds 3b, 4a, 6c and 6d were also characterised crystallographically. 相似文献
11.
Stefan Köcher Anthony L. Spek Tobias Rüffer Gerard van Koten 《Journal of organometallic chemistry》2008,693(13):2244-2250
The oxime-substituted NCN-pincer molecules HONCH-1-C6H3(CH2NMe2)2-3,5 (2a) and HONCH-4-C6H2(CH2NMe2)2-2,6-Br-1 (2b) were accessible by treatment of the benzaldehydes H(O)C-4-C6H3(CH2NMe2)2-3,5 (1a) and H(O)C-4-C6H2(CH2NMe2)2-2,6-Br-1 (1b) with an excess of hydroxylamine. In the solid state both compounds are forming polymers with intermolecular O-H?N connectivities between the Me2NCH2 substituents and the oxime entity of further molecules of 2a and 2b, respectively. Characteristic for 2a and 2b is a helically arrangement involving a crystallographic 21 screw axis of the HONCH-1-C6H3(CH2NMe2)2-3,5 and HONCH-4-C6H2(CH2NMe2)2-2,6-Br-1 building blocks.The reaction of 2b with equimolar amounts of [Pd2(dba)3 · CHCl3] (3) (dba = dibenzylidene acetone) or [Pt(tol)2(SEt2)]2 (4) (tol = 4-tolyl) gave by an oxidative addition of the C-Br unit to M coordination polymers with a [(HONCH-4-C6H2(CH2NMe2)2-2,6)MBr] repeating unit (5: M = Pd, 6: M = Pt). Complexes 5 and 6 are in the solid state linear hydrogen-bridged polymers with O-H?Br contacts between the oxime entities and the metal-bonded bromide. 相似文献
12.
The dipalladium complexes, [PdCl(μ-MeN{P(OR)2}2)]2 (R = CH2CF3, 1a; Ph, 1b) react with [Mo2(η5-C5H5)2(CO)6] in boiling benzene to afford the molybdenum-palladium heterometallic complexes, [(η5-C5H5)(CO)Mo(μ-MeN{P(OR)2}2)2PdCl] (R = CH2CF3, 3a; Ph, 3b), [(η5-C5H5)Mo(μ3-CO)2(μ-MeN{P(OR)2}2)2Pd2Cl], (R = CH2CF3, 5a; Ph, 5b), [(η5-C5H5)(Cl)Mo(μ2-CO)(μ2-Cl)(μ-MeN{P(OR)2}2)PdCl], (R = CH2CF3, 6a; Ph, 6b) and also the mononuclear complex [Mo(CO)Cl(η5-C5H5)(κ2-MeN{P(OR)2}2)], (R = Ph, 4b). These complexes have been separated by column chromatography and are characterised by elemental analysis, IR, 1H, 31P{1H} NMR data. The structures of 1a, 3a, 4b, 5b and 6a have been confirmed by single crystal X-ray diffraction. The CO ligands in 5b and 6a adopt a semi-bridging mode of bonding; the Mo-CO distances (1.95-1.97 Å) are shorter than the Pd-CO distances (2.40-2.48 Å). The Pd-Mo distances fall in the range, 2.63-2.86 Å. The reaction of [Mo2(η5-C5H5)2(CO)6] with MeN{P(OPh)2}2 in toluene gives [Mo2(CO)4(η5-C5H5)2(κ1-MeN{P(OPh)2}2)2] (2) in which the diphosphazane acts as a monodentate ligand. 相似文献
13.
The new ferrocenylmethylphosphines PH(CH2Fc)2 (1) [Fc = Fe(η5-C5H5)(η5-C5H4)] and P(CH2Fc)3 (2) and the phosphonium salt [P(CH2Fc)3(CH2OH)]I (3) were synthesised from P(CH2OH)3 and [FcCH2NMe3]I. [P(CH2Fc)(CH2OH)3]Cl (4) was obtained from P(CH2Fc)(CH2OH)2, CH2O and HCl. The new phosphines and phosphonium salts were fully characterised by NMR and IR spectroscopy and MS. [Mo(CO)6] reacts with 1 to give [Mo(CO)5{PH(CH2Fc)2}] (5) in high yield, but attempts to employ 2 as a ligand failed. The reaction of [P(CH2Fc)3(CH2OH)]I (3) and [PH(CH2Fc)3]I (obtained in situ from 3 and Na2S2O5) with [WI2(CO)3(NCMe)2] gave the complex salts [P(CH2Fc)3(CH2OH)][WI3(CO)4] (6) and [PH(CH2Fc)3][WI3(CO)4] (7), respectively. [P(CH2Fc)4]I (8) was synthesized from PH2CH2Fc and [FcCH2NMe3]I. Crystal structures were obtained for 1, 3-8. 相似文献
14.
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
15.
The reactions of ligands 4-C6H5C6H4CHNCH2CH2NMe2 (1a) and 2-C6H5C6H4CHNCH2CH2NMe2 (1b) in front of cis-[PtCl2(dmso)2] or cis-[PtPh2(SMe2)2] produced compounds [PtCl2{4-C6H5C6H4CHNCH2CH2NMe2}] (2aCl) and [PtCl2{2-C6H5C6H4CHNCH2CH2NMe2}] (2bCl) or [PtPh2{4-C6H5C6H4CHNCH2CH2NMe2}] (2aPh) and [PtPh2{2-C6H5C6H4CHNCH2CH2NMe2}] (2bPh). From all these compounds, the corresponding cyclometallated [C,N,N′] platinum(II) compounds 3aCl, 3bCl, 3aPh and 3bPh were obtained although under milder conditions and with higher yields for the phenyl derivatives. The reaction of compounds 3aPh and 3bPh with methyl iodide gave cyclometallated [C,N,N′] platinum(IV) compounds 4aPh and 4bPh of formula [PtMePhI{C6H5C6H3CHNCH2CH2NMe2}]. Compounds 3aCl and 3bCl containing a chloro ligand, although unreactive towards methyl iodide, undergo oxidative addition of chlorine to produce the corresponding platinum(IV) compounds [PtCl3{4-C6H5C6H3CHNCH2CH2NMe2}] (6aCl and 6bCl). All compounds were characterised by NMR spectroscopy and crystal structures of compounds 3bCl and 6bCl are also reported. 相似文献
16.
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
17.
The new ferrocenyl substituted ditertiary phosphine {FcCH2N(CH2PPh2)CH2}2 [Fc = (η5-C5H4)Fe(η5-C5H5)] (1) was prepared, in 72% yield, by Mannich based condensation of the known bis secondary amine {FcCH2N(H)CH2}2 with 2 equiv. of Ph2PCH2OH in CH3OH. Phosphine 1 readily coordinates to various transition-metal centres including Mo0, RuII, RhI, PdII, PtII and AuI to afford the heterometallic complexes {RuCl2(p-cym)}2(1) (2), (AuCl)2(1) (3), cis-PtCl2(1) (4), cis-PdCl2(1) (5), cis-Mo(CO)4(1) (6), trans,trans-{Pd(CH3)Cl(1)}2 (7) and trans,trans-{Rh(CO)Cl(1)}2 (8). In complexes 2, 3, 7 and 8 ligand 1 displays a P,P′-bridging mode whilst for 4-6 a P,P′-chelating mode is observed. All new compounds have been fully characterised by spectroscopic and analytical methods. Furthermore the structures of 1, 2 · 2CH2Cl2, 3 · CH2Cl2, 4 · CH2Cl2, 6 · 0.5CHCl3 and 8 have been elucidated by single crystal X-ray crystallography. Electrochemical measurements have been undertaken, and their redox chemistry discussed, on both noncomplexed ligand 1 and representative compounds containing this new ditertiary phosphine. 相似文献
18.
Anikó Nemes 《Journal of fluorine chemistry》2010,131(12):1368-1376
2,2,2-Trifluoroethanol, 1,1,1,3,3,3-hexafluoro-2-propanol, and nonafluoro-tert-butyl alcohol were used as precursors for the preparation of the appropriate bis(polyfluoroalkoxymethyl)carbinols [(RFHOCH2)2CHOH, 1a-c, RFH = (a) CF3CH2, (b) (CF3)2CH, and (c) (CF3)3C] and the corresponding mesylates [(RFHOCH2)2CHOSO2CH3, 2a-c]. This novel design paradigm is introduced to eliminate the persistence and bioaccumulation problems of fluorous chemistry, which are associated with the use of longer linear perfluoroalkyl groups (e.g. Rfn ≥ n-C8F17, n-C7F15). Secondary mesylates 2a,b and the primary tosylate [(CF3)3COCH2CH2OTs, 2d] displayed acceptable reactivity towards azide and imidazole nucleophiles to allow the syntheses of novel fluorous azides, which on hydrogenolysis with H2/Pd-C offered fluorous amines [(RFHOCH2)2CHNH2, 8a,b], and 1-(polyfluoroalkyl)imidazoles (5a,b,d), respectively, while 2c showed no reactivity due to steric hindrance. The reaction of 8a,b with formaline, glyoxal and hydrochloric acid gave symmetrical 1,3-dialkylated imidazolium chlorides (9a,b), while 5a,b,d were effectively alkylated using n-C8F17(CH2)3I, methyl iodide, 2-bromoethanol, and 2d to yield the corresponding 1,3-dialkylimidazolium iodides, bromides, and tosylates (7aa-ec). Some physical properties of new compounds including mp, bp and solubility patterns were also analyzed; and the fluorophilicity values of 1a-c, and 2a-c were experimentally determined by GC and/or 19F NMR spectroscopy. 相似文献
19.
New half-sandwich titanocene complexes (η5-C5Me5)Ti(OC6F5)3 (1), (η5-C5Me5)Ti(OCH2C6F5)3 (2), and (η5-C5Me5)Ti(OCH2C6F2H3)3 (3) were synthesized via the displacement of methoxide ligands in (η5-C5Me5)Ti(OMe)3 by the corresponding aryloxy or benzyloxy ligands. These compounds have been fully characterized by various spectroscopic methods including X-ray crystallography. Compound 1 has a distorted three-legged piano stool structure. However, complexes 2 and 3 have the chariot-like structure, where chariot means a two-wheeled horse-drawn vehicle. The π electron donation of oxygen atom to Ti center in complexes 1-3 is considerable. 相似文献
20.
《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