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1.
A study has been carried out of the catalytic activity of the systems formed by [HRh{P(OPh) 3} 4] or [HRh(CO){P(OPh) 3} 3] with the modifying ligands P(OPh) 3, PPh 3, diphos and Cp 2Zr(CH 2PPh 2) 2 in hydroformylation of hex-1-ene (at p = 5 bar). The best results were obtained with the system [HRh{P(OPh) 3} 4]+Cp 2Zr(CH 2PPh 2) 2 (75–85% yeild of aldehydes). 相似文献
2.
The compounds Cp 2VR (R = CH 3, C 2H 5, n-C 3H 7, n-C 4H 9, n-C 5H 11, CH 2C(CH 3) 3 or CH 2Si(CH 3) 3) have been prepared from Cp 2 VCl and RMgX in n-pentane. The air-sensitive compounds are stable at room temperature, but decompose between 65 and 138°C. The thermal stability decreases in the order R = CH 3 CH 2Si(CH 3) 3 > C 2H 5 > CH 2C(CH 3) 3 > n-C 5H 11 > n-C 4H 9 > n-C 3H 7. Compounds with R = i-C 3H 7 or t-C 4H 9 could not be obtained. 相似文献
3.
Synthesis of H 3Ru 3(μ 3-CSEt)(CO) 9, is accomplished by base-promoted attack of ethanethiol on H 3Ru 3(μ 3-CBr)(CO) 9. Thermolysis of this product under CO yields HRu 3(CH 2SEt)(CO) 9. Reactions of H 3Ru 3(μ 3-CSEt)(CO) 9 with alkynes C 2R 2 form HRu 3(μ 3-η 3-EtSCCRCR)(CO) 9 (R = Me or Ph) and Ru 3 ( cis-CR=CHR)(CSEt)(CO) 9 (R = Me). The chemistry of H 3Ru 3(μ 3-CSEt)(CO) 9 differs significantly from that of the analogous ether derivative H 3Ru 3(μ 3-COMe)(CO) 9. 相似文献
4.
Six new cluster derivatives [Rh 2Co 2(CO) 6(μ-CO) 4(μ 4,η 2-HCCR)] (R=FeCp 2 1, CH 2OH 2, (CH 3O)C 10H 6CH(CH 3)COOCH 2CCH 3) and [RhCo 3(CO) 6(μ-CO) 4(μ 4,η 2-HCCR)] (R=FeCp 2 4, CH 2OH 5, (CH 3O)C 10H 6CH(CH 3)COOCH 2CCH 6) were obtained by the reactions of [Rh 2Co 2(CO) 12] and [RhCo 3(CO) 12] with substituted 1-alkyne ligands HCCR [R=FeCp 2 7, CH 2OH 8, (CH 3O)C 10H 6CH(CH 3) COOCH 2CCH 9] in n-hexane at room temperature, respectively. Alkynes insert into the Co---Co bond of the tetranuclear clusters to give butterfly clusters. [Rh 2Co 2(CO) 6(μ-CO) 4(μ 4,η 2-HCCFeCp 2)] (1) was characterized by a single-crystal X-ray diffraction analysis. Reactions of 1, 2 with 7, 8 and ambient pressure of carbon monoxide at 25 °C gave two known cluster complexes [Co 2(CO) 6(μ 2, η 2-HCCR)] (R=FeCp 2 10, CH 2OH 11), respectively. All clusters were characterized by element analysis, IR and 1H-NMR spectroscopy. 相似文献
5.
Hydrogensulfido and hydrogenselenido complexes of general composition (η 5-C 5R 5(CO)3M(EH) (R = H, CH 3; M = Cr, Mo, W; E = S, Se) react at the EH functions by deprotonation, bimolecular elimination of H 2E, or by loss of the chalcogen atoms E. Reactions with Lewis-acidic complex cations such as [((η 5-C 5R 5)(CO) 3M] + (R = H, CH 3; M = Mo, W) are useful for the synthesis of chalcogen bridged compounds (μ-E)[(η 5-C 5R 5)(CO) 3M] 2. The heterodinuclear chalcogen bridge complexes thus generated form metathesis equilibria with their corresponding homodinuclear systems. 相似文献
6.
Hydrogenchalcogenido complexes of general composition (η 5-C 5R 5)(CO) 3M(EH) (R = H, CH 3; M = Cr, Mo, W; E = S, Se) can be obtained by three different routes, sometimes in quite good yields. Thus, the sulfur and selenium derivatives can be synthesized by insertion of the respective elements into the metal-hydrogen bonds of the precursor compounds (η 5-C 5R 5)(CO) 3MH. This species also reacts with potassium selenocyanate to yield the hydrogenselenido derivatives (η 5-C 5R 5)(CO) 3M(SeH) which can also be obtained by treatment of the methyl complexes (η 5-C 5R 5)(CO) 3M(CH 3 (M = Mo, W) with HBF 4 and Li[SeH]. The corresponding hydrogentellurido compounds are probably formed by these preparative methods but appear to be quickly converted into either the dinuclear tellurium bridge products (μ-Te)[(η 5-C 5R 5)(CO) 3M] 2 (M = Mo) or into the hydrido complexes (η 5-C 5R 5)(CO) 3MH (M= Mo, W) by release of elemental tellurium. 相似文献
7.
Reaction of [Cp *TiF 3] (Cp * = (ν 5-C 5Me 5)) with Me 3SiOSO 2- p-C 6H 4CH 3, Me 3SiOPOPh 2 and 1,2-(Me 3SiOCO) 2C 6H 4 yields the dinuclear complexes [{Cp *TiF(μ-F)(μ-OSO 2- p-C 6H 4CH 4)} 2] (1), [{Cp *TiF(μ-F)(μ-OPOPh 2)} 2] (2) and [{Cp *TiF(μ-F)(μ-OCO- o-C 6H 4CO 2SiMe 3)} 2] (3). The molecular structures of 1 and 2 have been determined by single-crystal X-ray analysis. In complexes 1-3, the two titanium atoms are connected by bridging fluorine atoms as well as bridging sulfonate, phosphinate and carboxylate groups respectively. Each titanium atom is also bonded to a terminal fluorine atom. Reaction of [Cp 2*ZrF 2] with 1,2-(Me 3SiOCO) 2C 6H 4 leads to the mononuclear pentacoordinate 18-electron species [Cp 2*ZrF(μ-OCO- o-C 6H 4CO 2SiMe 3)] (4) and its structure was determined by X-ray crystallographic methods. 相似文献
8.
While each of the three organosamarium(III) title complexes: [Cp 2Sm{μ-OC 10H 19}] 2 (5; Cp = C 5H 5, OC 10H 19 = isomenthoxide), [Cp 2Sm{μ-OCH(Me)COO iBU}] 2 (6) and [Cp 3SmOS(Me)- p-C 6H 4Me] (7) contains a chiral ligand atom (i.e. C or S) next to the metal-bonded oxygen atoms, only the dinuclear compounds 5 and, even better, 6 display (below ca. 600 nm) significant circular dichroism of discrete f---f-crystal field transitions. According to a successful single-crystal X-ray study of 5, the cyclohexyl ring of its (1S,2R,5R)-isomenthoxide ligand adopts a conformation with axial OSm- and iPr-substituents, which is energetically less favourable at least for neat (1S,2R,5R)-isomenthol. ZusammenfassungObwohl jeder der drei neuen Organosamarium(III)-Komplexe: [Cp2Sm{μ-OC10OH19}]2 (5; Cp = C5H5, OC10H19 = Isomentholat), [Cp2Sm{μ-OCH(Me)COOiBU}]2 (6) und [Cp3SmOS(Me)-p-C6H4Me] mindestens ein chirales Ligandenatom (C oder S) unmittelbar am metallkoordinierten O-Atom enthält, zeigen nur die dimeren Systeme 5 und noch ausgeprägter 6 (unterhalb von ca. 600 nm) signifikanten Circulardichroismus von f---f-Kristallfeldübergängen des Sm3+-Ions. Auf Grund einer erfolgreichen Kristallstrukturanalyse von 5 liegt der Cyclohexylring des (1S,2R,5R)-Isomentholatliganden ausschließlich in der Konformation mit axialen OSm- und iPr-Substituenten vor, die für freies (1S,2R,5R)-Isomenthol energetisch deutlich unvorteilhafter ist. 相似文献
9.
The reaction of [Cp 2MoH 2] and AgBF 4 with the dithio ligands Na(S 2CPh) and K(S 2CO iPr) afforded the complexes [(Cp 2MoH 2AgS 2CPh) 2] (1) and [(Cp 2MoH 2AgS 2CO iPr) 2] (2). Using the monothio ligands Na(SC(O)Ph), K(SC(O)CH 3) and Na(S(NHPh)C=C(CN) 2) the complexes [(Cp 2MoH 2AgSC(O)Ph) 2] (3), [((Cp 2MoH 2) 2(AgSC(O)CH 3) 3) n] (4) and [(Cp 2MoH 2) 2AgS(NHPh)C=C(CN) 2] (6) were formed. The reaction of thiobenzamide and [(Cp 2MoH 2) 2AgCl] gave the complex [(Cp 2MoH 2Ag(Cl)S(NH 2)CPh) 2] (5). Complexes 1 and 2 have a dimeric structure with the two dithio ligands bridging the two silver atoms. Complex 3 is also a dimer, however, the monothio ligands are coordinated with their single sulphur atoms to the silver atoms. In the polymer 4 the thioacetate ligand has the same bonding mode as in 3. The three-dimensional structure of 4 is built-up of parallel strings. In the dimer 5 the thiobenzamide ligands bind with the sulphur atom to a silver atom each. Complex 6 has a monomeric structure in which the silver atom is coordinated to two [Cp 2MoH 2] ligands and to the sulphur atom of the S(NHPh)C=C(CN) 2 ligand. Compounds 1–6 were characterised analytically and spectroscopically and the structures were determined by single crystal X-ray analyses. 相似文献
10.
The new terminal phosphinidene complex [Cp 2Zr=PDmp(PMe 3)] (Dmp=2,6-Mes 2C 6H 3; 1) was prepared in 81% yield by the reaction of [Li(Et 2O)][P(H)Dmp] with [Cp 2Zr(Me)Cl] in the presence of excess PMe 3. Compound 1 reacts with Ph 2PCl to produce selectively the sterically congested triphosphane DmpP(PPh 2) 2 (2) and [Cp 2ZrCl 2] in high yields. The structure of 2 obtained by X-ray diffraction analysis of a single crystal reveals phosphorus–phosphorus bond lengths of 2.251(2) and 2.234(2) Å and a PPP bond angle of 105.46(6)°. 相似文献
11.
Three families of heterobimetallic compounds were obtained by reaction of [Mo(CO) 3(CH 3CN) 2(Cl)(SnRCl 2)] (R = Ph, Me) with P(4-XC 6H 4) 3 (X = Cl, F, H, Me, MeO). The type of compound obtained dependent on the solvent and concentration of the starting compound. So, [Mo(CO) 2(CH 3COCH 3) 2(PPh 3)(Cl)(SnRCl 2)]· nCH 3COCH 3 (R = Ph, n = 0.5; R = Me, n = 1) (type I) and [Mo(CO) 3{P(4-XC 6H 4) 3}(μ-Cl)(SnRCl 2)] 2 (R = Ph, X = Cl, F, H, Me, MeO; R = Me, X = Cl, F) (type II) were isolated from acetone solution in ca 0.05 M and 0.1 M concentrations, respectively. However, [Mo(CO) 3(CH 3CN) {P(4-XC 6H 4) 3}(Cl)(SnRCl 2)] (R = Ph, X = H; R = Me, X = Cl, F, H) (type III) were obtained from dichloromethane solution independently of the concentration used. All new complexes showed a seven-coordinate environment at molybdenum, containing Mo---Cl and Mo---Sn bonds. Mössbauer spectra indicated a four-coordination at tin for type III complexes. 相似文献
12.
Oxidative addition of ethyl iodide to PdMe 2(2,2′-bipyridyl) in (CD 3) 2CO gives the unstable “PdIMe 2Et(bpy)”, which undergoes reductive elimination to form PdIR(bpy) (R = Me, Et), ethane, and propane. Ethene and palladium metal are also formed, and are attributed to decomposition of PdIEt(bpy) via β-elimination. Similar results are obtained with n-propyl iodide, although a palladium(IV) intermediate was not detected, but CH 2=CHCH 2X (X = Br, I) and PhCH=CHCH 2Br give isolable complexes fac-PdXMe 2(CH 2CH=CHR)(L 2) (R = H, Ph; L 2 = bpy, phen). The propenyl complexes decompose at ambient temperature to form ethane, a trace of PdXMe(L 2), and mixtures of [Pd(η 3-C 3H 5)(L 2)]X and [Pd(η 3-C 3H 5)(L 2)]-[Pd(η 3-C 3H 5)X 2]; for fac-PdBrMe 2(CH 2CH=CH 2)(bpy) the major palladium(II) product is [Pd(η 3-C 3H 5)(bpy)]Br. 相似文献
13.
Cp 2MoH 2 reacts with methyl acrylate in the presence of acetylenes (L = C 2H 2, C 2Me 2, HCC tBu, HCCSiMe 3, C 2(SiMe 3) 2, HCCCH 2OMe, HCCCH 2NMe 2) to form acetylene complexes Cp 2Mo(L) 5. Protonation takes place with CF 3CO 2H at −80°C to give short-lived cations [Cp 2MoH(L) + (8) (L = C 2Me 2, HCCSiMe 3, C 2(SiMe 3) 2). The structure of [Cp 2MoH{η 2-C 2(SiMe 3) 2}]PF 6(9) was determined by an X-ray diffraction study. 相似文献
14.
The heterobimetallic trinuclear sulfido clusters [(Cp*Ir) 2(μ 3-S) 2MCl 2] (M=Pd (3), Pt (4); Cp*=η 5-C 5Me 5) were synthesized from the dinuclear hydrogensulfido complex [Cp*IrCl(μ-SH) 2IrCp*Cl] (2) and [MCl 2(COD)] (COD=cycloocta-1,5-diene), while the reaction of 2 with [Pd(PPh 3) 4] afforded the cationic trinuclear cluster [(Cp*Ir) 2(μ 3-S) 2PdCl(PPh 3)]Cl (5). Clusters 3 and 4 reacted with PPh 3 to give a series of mono and dicationic clusters including 5, while the dicationic clusters [(Cp*Ir) 2(μ 3-S) 2M(dppe)][BPh 4] 2 (M=Pd (9), Pt (10); DPPE=Ph 2PCH 2CH 2PPh 2) were obtained by the reaction with dppe followed by anion metathesis. The molecular structures of 5·CH 2Cl 2, 9·CH 3COCH 3, and 10·CH 3COCH 3 were determined by X-ray crystallography. Clusters 3 and 4 were found to catalyze the addition of alcohols to alkynes to give the corresponding acetals. Internal 1-aryl-1-alkynes were transformed by cluster 3 into the corresponding 2,2-dialkoxy-1-arylalkanes with high regioselectivity up to 99:1, while cluster 4 was a much less regioselective catalyst. 相似文献
15.
The reaction of imidoylzirconocene complexes with zirconocene hydrides yields ( N-alkylamido)zirconocene complexes. For a mechanistic study, the specifically substituted imidoylzirconocene complexes 3b–3d have been prepared and treated with the oligomeric metal hydrides (Cp 2ZrH 2) x (1b) and (Cp 2ZrHCl) x (1c). ( N-Benzyl formimidoyl)zirconocene chloride (3b) was obtained by treating 1c with benzyl isonitrile 2a. Treatment of dimethylzirconocene with 2a gave ( N-benzyl acetimidoyl)methylzirconocene (3c), which was treated with PhICl 2 to give ( N-benzylacetimidoyl)zirconocene chloride (3d). The reaction of 3d with (Cp 2ZrH 2) x (1b) yielded ( N-benzyl- N-ethylamido)zirconocene chloride (4b) as the only identified product. A 1/1 mixture of 4b and methylzirconocene chloride was obtained upon treatment of 3c with (Cp 2ZrHCl) x (1c); in contrast, the reaction of 1c with 3b gave an equimolar mixture of Cp 2ZrCl 2 and ( N-benzyl- N-methylamido)zirconocene chloride (4c). Reaction paths through binuclear (μ-CHR′=NR) zirconocene intermediates are proposed to explain these experimental observations. 相似文献
16.
Reactions of -, β- and γ-hydrogen elimination in cyclopentadienylnickel compounds formed in the reactions of nickelocene with lithium or magnesium compounds are discussed. Elimination of -hydrogen from CpNiR where R is CH 3, CH 2C(CH 3) 3, CH 2Si(CH 3) 3, CH 2Ph or CH=C(CH 3) 2 leads to the formation of trinickel clusters (CpNi) 3CR′, bis(cyclopentadienyl)(μ-cyclopentadiene)dinickel and (η 5-cyclopentadienyl)(η 3-cyclopenteny)nickel. β-hydrogen and γ-hydrogen elimination in vinylnickel compounds not possesing -hydrogen have been studied. Elimination and transfer of hydrogen forms (η 3-allyl)(η 5-cyclopentadienyl)nickel compounds. The mechanisms of these reactions are discussed. 相似文献
17.
The reaction of the metallocene dichlorides Cp 2MCl 2 (Cp = η 5-C 5H 5; M = Ti, Zr, Hf, Mo, W) and Cp 2′TiCl 2 (Cp′ = η 5-C 5H 4CH 3) with equimolar amounts of dilithium-benzene- o-diselenolate, 1,2-(LiSe) 2C 6H 4, gives the chelate complexes Cp 2M(Se 2C 6H 4) (M = Ti (I), Zr (II), Hf (III), Mo (IV), W (V)) and Cp 2′Ti(Se 2C 6H 4) (VI). CpTiCl 3 reacts with 1,2-(LiSe) 2C 6H 4 to give CpTiCl(Se 2C 6H 4) (VII). The ring inversion activation parameters for I–VI can be determined by means of temperature-dependent 1H NMR spectroscopy in solution. The fragmentation behaviour of I–VII in the mass spectrometer has been investigated by pursuing metastable transitions, using linked-scan techniques. 相似文献
18.
Recent results (post-1990) on the synthesis and structures of bis(trimethylsilyl)methyls M(CHR 2) m (R = SiMe 3) of metals and metalloids M are described, including those of the crystalline lipophilic [Na(μ-CHR 2)] ∞, [Rb(μ-CHR 2)(PMDETA)] 2, K 4(CHR 2) 4(PMDETA) 2, [Mg(CHR 2)(μ-CHR 2)] ∞, P(CHR 2) 2 (gaseous) and P 2(CHR 2) 4, [Yb(CHR 2) 2(OEt 2) 2] and [{Yb(CR 3)(μ-OEt)(OEt 2)} 2]; earlier information on other M(CHR 2) m complexes and some of their adducts is tabulated. Treatment of M(CHR 2) (M = Li or K) with four different nitriles gave the X-ray-characterized azaallyls or β-diketinimates
,
and
(LL′ = N(R)C( tBu)CHR, L′L′ = N(R)C(Ph)C(H)C(Ph)NR, LL″ = N(R)C(Ph)NC(H)C(Ph)CHR, R = SiMe 3 and Ar = C 6H 3Me 2-2,5). The two lithium reagents were convenient sources of other metal azaallyls or β-diketinimates, including those of K, Co(II), Zr(IV), Sn(IV), Yb(II), Hf(IV) and U(VI)/U(III). Complexes having one or more of the bulky ligands [LL′] −, [L′L′] −, [LL] −, [LL″] −, [L″L] −, [LL] − and [{N(R)C( tBu)CH} 2C 6H 4-2] 2− are described and characterized (LL = N(H)C(Ph)C(H)C(Ph)NH, L″L = N(R)C( tBu)C(H)C(Ph)NR, LL = N(R)C( tBu)CHPh). Among the features of interest are (i) the contrasting tetrahedral or square-planar geometry for
and
, respectively, and (ii) olefin-polymerization catalytic activity of some of the zirconium(IV) chlorides. 相似文献
19.
The reaction of the anionic mononuclear rhodium complex [Rh(C 6F 5) 3Cl(Hpz)] t- (Hpz = pyrazole, C 3H 4N 2) with methoxo or acetylacetonate complexes of Rh or Ir led to the heterodinuclear anionic compounds [(C 6F 5) 3Rh(μ-Cl)(μ-pz)M(L 2)] [M = Rh, L 2 = cyclo-octa-1,5-diene, COD (1), tetrafluorobenzobarrelene, TFB (2) or (CO) 2 (4); M = Ir, L 2 = COD (3)]. The complex [Rh(C 6F 5) 3(Hbim)] − (5) has been prepared by treating [Rh(C 6F 5) 3(acac)] − with H 2bim (acac = acetylacetonate; H 2bim = 2,2′-biimidazole). Complex 5 also reacts with Rh or Ir methoxo, or with Pd acetylacetonate, complexes affording the heterodinuclear complexes [(C 6F 5) 3Rh(μ-bim)M(L 2)] − [M = Rh, L 2 = COD (6) or TFB (7); M = Ir, L 2 = COD (8); M = Pd, L 2 = η 3-C 3H 5 (9)]. With [Rh(acac)(CO) 2], complex 5 yields the tetranuclear complex [{(C 6F 5) 3Rh(μ-bim)Rh(CO) 2} 2] 2−. Homodinuclear Rh III derivatives [{Rh(C 6F 5) 3} 2(μ-L) 2] ·- [L 2 = OH, pz (11); OH, S tBu (12); OH, SPh (13); bim (14)] have been obtained by substitution of one or both hydroxo groups of the dianion [{Rh(C 6F 5) 3(μ-OH)} 2] 2− by the corresponding ligands. The reaction of [Rh(C 6F 5) 3(Et 2O) x] with [PdX 2(COD)] produces neutral heterodinuclear compounds [(C 6F 5) 3Rh(μ-X) 2Pd(COD)] [X = Cl (15); Br (16)]. The anionic complexes 1–14 have been isolated as the benzyltriphenylphosphonium (PBzPh 3+) salts. 相似文献
20.
Reactions of FcCCH (a), HCCCCFc (b) and FcCCCCFc (c) with Ru 3(CO) 10(NCMe) 2 (all) and Ru 3(μ-dppm)(CO) 10 (b and c only) are described. Among the products, the complexes Ru 3(μ 3-RC 2R′)(μ-CO)(CO) 9 (R=H, R′=Fc 1, CCFc 2; R=R′=Fc 5), Ru 3(μ-H)(μ 3-C 2CCFc)(μ-dppm)(CO) 7 3, Ru 3(μ 3-FcC 2CCFc)(μ-dppm)(μ-CO)(CO) 7 6 and Ru 3{μ 3-C 4Fc 2(CCFc) 2}(μ-dppm)(μ-CO)(CO) 5 7 were characterised, including single-crystal structure determinations for 1, 3, 5 and 7; that of 7 did not differ significantly from an earlier study of a mixed CH 2Cl 2–C 6H 6 solvate. 相似文献
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