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1.
Thermal displacement of coordinated nitriles RCN (R = CH 3, C 2H 5 or n-C 3H 7) in [C 5H 5Fe(L 2)(NCR)]X complexes (L 2 = P(OCH 3) 3) 2, (P(OC 6H 5) 3) 2 or (C 6H 5) 2PC 2H 4P(C 6H 5) 2 (DPPE)) by E(CH 3) 2 affords high yields of [C 5H 5Fe(L 2)(E(CH 3) 2)]X compounds (E = S, Se and Te; X = BF 4 or PF 6). Spectroscopic data and ligand displacement reactions are presented and discussed together with related observations on [C 5H 5Fe(CO) 2(E(CH 3) 2)]BF 4 compounds. The molecular structure of [C 5H 5Fe(P(OCH 3) 3) 2(S(CH 3) 2)]PF 6 was determined by a single-crystal X-ray diffraction study: monoclinic, space group P2 1/ n- C52h (No. 14) with a = 8.4064(12), b = 11.183(2), c = 50.726(8) Å, β = 90.672(13)° and Z = 8 molecules per unit cell. The coordination sphere of the iron atom is pseudo-tetrahedral with an Fe---S bond distance of 2.238 Å. 相似文献
2.
A series of heterodimetallic complexes of general formula (C 5R 5)M(μ-CO) 3RuC 5Me 5 (M = Cr, Mo, W; R = Me, Et) has been prepared in good yields by the reaction of [C 5R 5M(CO) 3] − with [C 5Me 5Ru(CH 3CN) 3] +. (C 5Me 4Et)W(μ-CO) 3Ru(C 5Me 5) was characterized by a crystal structure determination. The W---Ru bond length of 2.41 Å is consistent with the formulation of a metal-metal triple bond, while the unsymmetrical bonding mode of the three bridging carbonyl groups reflects the inherent non-equivalence of the two different C 5R 5M-units. Using [CpRu(CH 3CN) 3] + or [CpRu(CO) 2(CH 3CN)] + as the cationic precursor leads to the formation of dimetallic species (C 5R 5)M(CO) 5RuC 5H 5 with both bridging and terminal carbonyl groups. 相似文献
3.
The electron donating water soluble phosphines, P{(CH 2) nC 6H 4- p-SO 3Na} 3, n = 1, 2, 3 and 6, react rapidly with Co 2(CO) 8 under two phase reaction conditions to yield the disproportionation products, [Co(CO) 3(P{(CH 2) nC 6H 4- p-SO 3Na 3} 2] [Co(CO) 4]. Selective precipitation yields the formally zwitterionic complex anions as the sodium salt, [Co(CO) 3(P{(CH 2) nC 6H 4- p-SO 3} 3) 2] 5−. The anions can be used as precursors to water soluble cobalt hydroformylation catalysts under two phase and supported aqueous phase conditions. The tendency to form alcohol products is low with these complexes. The behavior of the catalysts is consistent with an active species that remains water soluble during the reaction and is not leached into the nonaqueous phase. 相似文献
4.
The P-functional organotin dichloride [Ph 2P(CH 2) 3] 2SnCl 2 (3) is synthesized by reaction of Ph 2P(CH 2) 3MgCl with SnCl 4 independently of the molar ratio of the starting compounds. The corresponding organotin trichlorides Ph 2P(CH 2) nSnCl 2R (4: n=2, R=Cl; 5: n=3, R=Cl; 6: n=3, R=Me) are formed in a cleavage reaction of Ph 2P(CH 2) nSnCy 3 ( n=2, 3) with SnCl 4 or MeSnCl 3, respectively. The main features of the crystal structures of 3–6 are both intra- and intermolecular PSn coordinations and the existence of intermolecular Sn---ClSn bridges. For further characterization of the title compounds, the adducts 4(Ph 3PO) 2 (7) and 5(Ph 3PO) (8), as well as the P-oxides and P-sulfides of 3–6 (9–15), are synthesized. The results of crystal structure analyses of 7, 11, 12, and 14 are reported. The structures of 9–15 are characterized by intramolecular P=XSn interactions (X=O, S). A first insight into the structural behavior of the compounds 3–15 in solution is discussed on the basis of multinuclear NMR data. 相似文献
5.
Treatment of ruthenium complexes [CpRu(AN) 3][PF 6] (1a) (AN=acetonitrile) with iron complexes CpFe(CO) 2X (2a–2c) (X=Cl, Br, I) and CpFe(CO)L′X (6a–6g) (L′=PMe 3, PMe 2Ph, PMePh 2, PPh 3, P(OPh) 3; X=Cl, Br, I) in refluxing CH 2Cl 2 for 3 h results in a triple ligand transfer reaction from iron to ruthenium to give stable ruthenium complexes CpRu(CO) 2X (3a–3c) (X=Cl, Br, I) and CpRu(CO)L′X (7a–7g) (L′=PMe 3, PMe 2Ph, PMePh 2, PPh 3, P(OPh) 3; X=Br, I), respectively. Similar reaction of [CpRu(L)(AN) 2][PF 6] (1b: L=CO, 1c: P(OMe) 3) causes double ligand transfer to yield complexes 3a–3c and 7a–7h. Halide on iron, CO on iron or ruthenium, and two acetonitrile ligands on ruthenium are essential for the present ligand transfer reaction. The dinuclear ruthenium complex 11a [CpRu(CO)(μ-I)] 2 was isolated from the reaction of 1a with 6a at 0°C. Complex 11a slowly decomposes in CH 2Cl 2 at room temperature to give 3a, and transforms into 7a by the reaction with PMe 3. 相似文献
6.
The compounds (π-C 5H 5)(CO) 2LM-X (L = CO, PR 3; M = Mo, W; X = BF 4, PF 6, AsF 6, SbF 6) react with H 2S, p-MeC 6H 4SH, Ph 2S and Ph 2SO(L′) to give ionic complexes [(π-C 5H 5)(CO) 2LML′] + X −. Also sulfur-bridged complexes, [(π-C 5H 5)(CO) 3W---SH---W(CO) 3(π-C 5H 5)] + AsF 6− and [(π-C 5H 5)(CO) 3M-μ-S 2C=NCH 2Ph-M(CO) 3(π-C 5H 5)], have been obtained. Reactions with SO 2 and CS 2 have been examined. 相似文献
7.
The title compounds react with unidentate ligands, L, containing either phosphorus or arsenic donor atoms to yield the corresponding compounds of the type Ru(η 5---C 5Me 4Et)(CO)LX; with didentate phosphorus donor ligands the major species formed is the bridged complex {Ru(η 5---C 5Me 4Et)(CO)X} 2{Ph 2P(CH 2) nPPh 2} n = 1, X = Br; n = 2, X = Cl). In contrast, unidentate ligands containing nitrogen donor atoms such as pyridine did not react with Ru(η 5---C 5Me 4Et)(CO) 2Cl although reaction with 1,10-phenanthroline or diethylenetriamine yielded the ionic products [Ru(η 5---C 5Me 4Et)(CO)L] +Cl − (L = phen or (NH 2CH 2CH 2) 2NH). Reaction of Ru(η 5---C 5Me 4Et)(CO) 2Br with AgOAc yielded the corresponding acetato complex Ru(η 5---C 5Me 4Et)(CO) 20Ac. Ru(η 5--- C 5Me 4Et)(CO) 2X reacts with AgY (Y = BF 4 or PF 6) in either acetone or dichloromethane to give the useful solvent intermediates [Ru(η 5---C 5Me 4Et)(CO) 2(solvent)] +Y −, which readily react with ligands L to yield ionic derivatives of the type [Ru(η 5---C 5Me 4Et)(CO) 2L] +Y − (where L = CO, NCMe, py, C 2H 4 or MeO 2CCCCO 2Me). 相似文献
8.
A series of novel arylantimony(V) triphenylgermanylpropionates with the formula (Ph 3GeCHR 1CHR 2CO 2) nSbAr (5−n) (R 1=H, Ph; R 2=H, CH 3; n=1, 2) were synthesized and characterized by elemental analysis, IR, 1H-NMR, 13C-NMR and mass spectroscopy. The crystal structures of Ph 3GeCH(Ph)CH 2CO 2SbPh 4 and [Ph 3GeCH 2CH(CH 3)CO 2] 2Sb(4-ClC 6H 4) 3 were determined by X-ray diffraction. The in vitro antitumor activities of some selected compounds against five cancer cells are reported. 相似文献
9.
The ruthenium(II) complex Ru(CO) 2(NH 2(NH 2CH 2C 6H 5) 2(Si(C 6H 5)(CH 3) 2)I has been prepared by the reaction of Ru(CO) 4(Si(C 6H 5)(CH 3) 2)I with benzylamine. Two-dimensional homonuclear 1H NMR experiments examine the scalar coupling of the enantiotopic amino and methylene protons of the benzylamine ligand. X-ray analysis of Ru(CO) 2(NH 2CH 2C 6H 5) 2(Si(C 6H 5)(CH 3) 2)I·1/3C 5H 12 (triclinic; P
; a = 14.266(4), b = 15.748(5), c = 20.082(6) Å; = 94.38(3), β = 96.30(2), γ = 101.52(2)°) indicates three crystallographically unique complexes form a clathrate with a pentane guest. 相似文献
10.
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
11.
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
12.
Reaction of optically active ketone complexes (+)-( R)-[(η 5-C 5H 5)Re(NO)-(PPh 3)(η 1-O=C(R)(CH 3)] + BF 4− (R = CH 2CH 3, CH(CH 3) 2m C(CH 3) 3, C 6H 5) with K(s-C 4H 9) 3BH gives alkoxide complexes (+)-( RS)-(η 5-C 5H 5)Re(NO)(PPh 3)-(OCH(R)CH 3) (73–90%) in 80–98% de. The alkoxide ligand is then converted to Mosher esters (93–99%) of 79–98% de. 相似文献
13.
The reactions between [M(NO){HB(3,5-Me 2C 3HN 2) 3}X 2] (M = Mo, X = Cl, Br, I; M = W, X = Cl) and the monosaccharides 2,3:4,5-di-O-iso-propylidene-β-
-fructopyranose, 2,3:5,6-di-O-isopropylidene--
-mannofuranose, methyl--
-glucopyranoside and
-(+)-mannofuranose have been investigated and the complexes [M(NO){HB(3,5- Me 2C 3HN 2) 3}X(OR)] (M = Mo, X = Cl, Br, I; M = W, X = Cl; ROH = 2,3:4,5-di-O- isopropylidene-β-
-fructopyranose) have been isolated as mixtures of diastereoisomers. 相似文献
14.
The interaction of [(η 5-C 5H 4Bu t) 2YbCl · LiCl] with one equivalent of Li[(CH 2) (CH 2)PPh 2] in tetrahydrofuran gave [Ph 2PMe 2][(η 5-C 5H 4Bu t) 2Li] (1) and [(η 5-C 5H 4Bu t) 2Yb(Cl)CH 2P(Me)Ph 2] (2) in 10% and 30% yields, respectively. 1 could also be prepared in 70% yield from the reaction of [Ph 2PMe 2][CF 3SO 3] with two equivalents of (C 5H 4Bu t)Li. Both compounds have been fully characterized by analytical, spectroscopic and X-ray diffraction methods. The solid state structure of 1 reveals a sandwich structure for the [(η 5-C 5H 4Bu t) 2Li] − anion. 相似文献
15.
The preparation and properties as well as some reactions of a series of arylcarbonylbis(triphenylphosphine)iridium(I) complexes [Ir(Ar)(CO)(PPh 3) 2] (Ar = C 6H 5, C 6F 5, 2-C 6H 4CH 3, 3-C 6H 4CH 3, 4-C 6H 4CH 3, 2-C 6H 4OCH 3, 2,6-C 6H 3-(OCH 3) 2, 4-C 6H 4N(CH 3) 2, 3-C 6H 4Cl, 4-C 6H 4Cl, 4-C 6H 4Cl, 3-C 6H 4CF 3, 4-C 6H 4CF 3) are described, and the most important IR data as well as the 31P NMR parameters of these, without exception trans-planar, compounds are given. Some of the complexes react with molecular oxygen to form well defined dioxygen adducts [Ir(Ar)(O2)(CO)(PPh3)2] (Ar = C6H5, 3-C6H4CH3, 4-C6H4CH3). Complexes with ortho-substituted aryl ligands are not oxygenated. This effect is referred to as a steric shielding of the metal center by the corresponding ortho-substituents. With SO2 the similar irreversible addition compound [Ir(4-C6H4CH3)-(SO2)(CO)(PPh3)2] is obtained. Sulfur dioxide insertion into the Ir---C bond cannot be observed. The first step of the reaction between [Ir(4-C6H4CH3)(CO)(PPh3)2] and hydrogen chloride involves an oxidative addition of HCl to give [Ir(H)(Cl)(4-C6-H4CH3)(CO)(PPh3)2]. Ir---C bond cleavage by reductive elimination of toluene from the primary adduct does not occur except at elevated temperature. 相似文献
16.
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
17.
Nine complexes(RC_5H_4)_2Ti(O_2CC_6H_4X)_2(R=H,CH_3;X=H,o-Cl,o-OH,o-NH_2,o-NHPh)have been conveniently prepared by the reaction of(RC_5H_4)_2TiCl_2 with 2 equiv.sodium salts of corresponding carboxylic acidin aqueous solution containing acetylacetone.The carboxylate ligands inthe complexes coordinate to titanium atom in monodentate mode. 相似文献
18.
Treatment of the complex Mo(Nmes)(O)Cl 2(dme) (mes=2,4,6-trimethylphenyl; dme=1,2-dimethoxyethane) with KTp Me2, NaCp and bipy gives the corresponding derivatives (Tp Me2)Mo(Nmes)(O)Cl (1), CpMo(Nmes)(O)Cl (2) and Mo(Nmes)(O)Cl 2(bipy) (3). Other oxo---imido compounds of composition Mo(Nmes)(O)(S 2CNR 2) 2 (R 2=C 4H 4 4, C 5H 10 5, iPr 2 6) can be obtained by reacting Mo(Nmes)(O)Cl 2(dme) with the appropriate dithiocarbamate salt. The NMR properties of 4–6 are consistent with the presence of two rapidly equilibrating dithiocarbamate ligands. The reaction of Mo(Nmes)(O)Cl 2(dme) with different Grignard reagents, Mg(R)X, produces the trialkyl imido complexes Mo(Nmes)R 3Cl (R=Me 7, CH 2C(Me) 2Ph 8, CH 2SiMe 3 9). 相似文献
19.
Members of the series of bridging diphosphine clusters [Os 3(CO) 10(diphos)] where diphos = Ph 2P(CH 2nPPh 2 [dppm ( n = 1), dppe ( n = 2), dppp ( n = 3), or dppb ( n = 4)] show interesting differences in their reactivity towards H + and H 2. Protonation leads to [Os 3(μ-H)(CO) 10(diphos)] + with the hydrides bridging the same osmium atoms as the diphos ligand when diphos is dppe, dppp, or dppb, whereas the hydride and dppm bridge different edges in [Os 39μ-H)(CO) 10(dppm)] +. Hydrogenation of the 1,2-diphos compounds leads to [Os 3(μ-H) 2(CO) 8(diphos)] (diphos = dppm, dppe, dppp) in good to excellent yield but the dppb analogue could not be made. Geometric and electronic factors affecting the ability to incorporate hydride ligands in these clusters are discussed. 相似文献
20.
Reaction of ansa-cyclopentadienyl pyrrolyl ligand (C 5H 5)CH 2(2-C 4H 3NH) (2) with Ti(NMe 2) 4 affords bis(dimethylamido)titanium complex [(η 5-C 5H 4)CH 2(2-C 4H 3N)]Ti(NMe 2) 2 (3) via amine elimination. A cyclopentadiene ligand with two pendant pyrrolyl arms, a mixture of 1,3- and 1,4-{CH 2(2-C 4H 3NH)} 2C 5H 4 (4), undergoes an analogous reaction with Ti(NMe 2) 4 to give [1,3-{CH 2(2-C 4H 3N)} 2(η 5-C 5H 3)]Ti(NMe 2) (5). Molecular structures of 3 and 5 have been determined by single crystal X-ray diffraction studies. 相似文献
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