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1.
《Journal of organometallic chemistry》1987,320(2):145-162
Oxidative cleavage of the FeFe bond in [C5H5Fe(CO)2]2 in the presence of alkylide-bridged diphosphanes LL (LL = (C6H5)2P(CH2)n(P(C6H5)2; n = 1–3), (C6H5)2PCH2As(C6H5)2 and dichalcogenodiphosphoranes (X)LL(X) ((X)LL(X) = (C6H5)2P(X)(CH2)n(X)P(C6H5)2; X O, S, Se; n = 1–3) yields the complexes [C5H5Fe(CO)2L′]BF4 (L′ = LL, (X)LL(X); X S, Se) in high yield. the complexes react with Ni(CO)4 under photochemical conditions to form [C5H5Fe(CO)2(μ-L′)Ni(CO)3]BF4 in quantitative yield, and lose a CO group under irradiation (λmax > 300 nm) to form the chelate compounds [C5H5Fe(CO)L′]BF4, which are isolable for L′ LL (P,As ligand) and (X)LL(X) (X = S, Se). Some substitution reactions with phosphanes are described. 相似文献
2.
Hans Schumann 《Journal of organometallic chemistry》1985,293(1):75-91
Reactions of reactive cyclopentadienyliron complexes C5H5Fe(CO)2I, [C5H5Fe(CO)2THF]BF4, [C5H5Fe(CO)((CH3)2S)2]BF4 and [C5H5Fe(p-(CH3)2C6H4)]PF6 with P(OR)3 as ligands (R = CH3, C2H5, i-C3H7 and C6H5) lead to the formation of the complex compounds C5H5Fe(CO)2?n(P(OR)3)nI and [C5H5Fe(CO)3?n(P(OR)3)n]X (n = 1, 2 and n = 1–3, X = BF4, PF6). Spectroscopic investigations (IR, 1H, 13C and 31P NMR) indicate an increase of electron density on the central metal with increasing substitution of CO groups by P(OR)3 ligands. The stability of the compounds increase in the same way. 相似文献
3.
The ditertiary phosphines (C6H5)2P(CH2)nP(C6H5)2 (n = 1 and 2), cis(C6H5)2PC2H2P(C6H5)2 and (C6H5)2PN(C2H5)P(C6H52 and the ditertiary arsines (C6H5)2As(CH2)nAs(C6H5)2 (n = 1 and 2) react with [Fe(CO)3SC6H5]2 to give a wide range of products, the nature of which depends on the reaction conditions and the ligand involved. Examples of the different types of comp isolated include, (i) Fe2(CO)5[(C6H5)2PCH2P(C6H5)2](SC6H5)2, in which the ligand acts as a monodentate, (ii) {[Fe(CO)2SC6H5]2[(C6H5)2PC2H4P(C6H5)2]}2, in which two [Fe(CO)2SC6H5]2 moieties are bridged by two diphosphine ligands, (iii) [Fe(CO)2SC6H5]2[(C6H5)2PN(C2H5)P(C6H5)2], in which the ligand bridges the two iron atoms, and (iv) Fe(CO)3(SC6H5)2Fe(CO)[(C6H5)2PC2H2P(C6H5)2], which contains the ligand chelated to a single iron atom. The tertiary phosphines PR3 (R=C2H5 and C6H5), phosphites P(OR′)3(R′ = CH3, C2H5, i-C3H7 and C6H5) and the stibine Sb(C6H5)3 bring about mono-, bis- or tris-substitution in [Fe(CO)3SC6H5]2 depending on the reaction conditions and the ligand involved. Whereas in solution [Fe(CO)2L(SC6H5)]2 [L = PR3 (R = C2H5 and C6H5), P(OC6H5)3 and Sb(C6H5)3] exist as a single isomer, [Fe(CO)2L′(SC6H5)]2 [L′=P(OR′)3 (R'=CH3, C2H5 and i-C3H7)] occur as a mixture of isomers. 相似文献
4.
William C. Kaska Dennis K. Mitchell R.F. Reichelderfer 《Journal of organometallic chemistry》1973,47(2):391-402
The displacement of tetrahydrofuran (THF) from W(CO)5(THF) with hexaphenylcarbodiphosphorane yields a compound with a carbon-metal bond (CO)5W C[P(C6H5)3]2. The in situ photolysis of tungsten hexacarbonyl and hexaphenylcarbodiphosphorane, however, yields a product (CO)5W?CC +P(C6H5)3. Ethylenebis(triphenylphosphine)platinum and hexaphenylcarbodiphosphorane in benzene yield a platinum containing heterocycle [(C6H5)3P]2-(C6H5)3. 相似文献
5.
The dinuclear complex [(h5-1-CH3-3-C6H5C5H3)Fe(CO)2]2 was synthesized by reaction of Fe2(CO)9 with 1-methyl-3-phenylcyclopentadiene; it was converted to (h5-1-CH3-3-C6H5C5H3)Fe(CO)2CH3 by reduction with sodium amalgam and addition of CH3l, and thence to (h5-1-CH3-3-C6H5C5H3)Fe(CO)[P(C6H5)3] (COCH3) (I) by reaction with P(C6H5)3. The acetyl I was separated into two diastereomerically related pairs of enantiomers. Ia and Ib, by a combination of column chromatography on alumina and crystallization from benzene/pentane. The photochemical decarbonylation of Ia and Ib in benzene or THF solution was examined by 1H NMR spectroscopy. This reaction proceeds with high stereospecificity (>84% retention or inversion) at the iron center to yield (h5-1-CH3-3-C6H8C5H3)Fe(CO)[P(C6H5)3]CH3(II), enriched in the diastereomerically related pairs of enantiomers, IIa and IIb, respectively. Since IIa and IIb epimerize under the photolytic conditions of decarbonylation, the actual stereospecificity of the conversion of I to II is higher than 84%, and likely 100%. This is supported by the data from kinetic studies of the decarbonylation of I and the epimerization of II, carried out under identical photolytic conditions. The implications of the foregoing results to the mechanism of the decarbonylation are considered. Also described herein is the synthesis of other complexes with two asymmetric centers of the general formula (h5-cyclopentadienyl)Fe(CO)(L)(COR) and (h5-cyclopentadienyl)Fe(CO)(L)R that contain either an unsymmetrically substituted h5-cyclopentadienyl ring or a chiral tertiary phosphine. 相似文献
6.
Oxidative addition of 1-chloro-1-nitroethane to trans-IrCl(CO)-[P(CH3)2C6H5]2 followed by treatment of the initial product with pyridine yields a new iridium(III) complex IrCl(py)[COC(NO2)CH3][P(CH3)2C6H5]2, whose structure has been confirmed by X-rays crystallography. Two intermediate products have been observed by NMR spectroscopy; their structures have been tentatively assigned. The reaction of the corresponding bromine derivatives yields two isomers of the composition IrBr2(CO)[CH(NO2)CH3][P(CH3)2C6H5]2, and these are not affected by pyridine. The reaction of 1-chloro-1-nitroethane with Pt[P(C6H5)3]4 takes a completely different course in that yields nitrorethane and cis-PtCl2[P(C6H5)3]2 as the main products, with no detectable formation of the products of oxidation addition. A brief mechanistic investigation points towards the participation of radicals and radical anions as transient intermediates and a mechanism is proposed which explains most of the experimental results. 相似文献
7.
The photochemical preparation of [M(CO)5(P(CCC6H5)n(C6H5)3-n], cis-[M(CO)4(PCCC6H5)n(C6H5)3-n] (M = Cr, W; n = 1,2,3) and fac-[Cr(CO)3(P(CCC6H5)(C6H5)3] by the corresponding substitution reactions of the hexacarbonyls is described. The IR and Raman spectra of the complexes in the region of the ν(CO) and ν(CC) vibrations and the 31P NMR spectra are discussed. 相似文献
8.
L.A. Fedorov P.V. Petrovskii E.I. Fedin N.K. Baranetskaya V.I. Zdanovich V.N. Setkina D.N. Kursanov 《Journal of organometallic chemistry》1975,99(2):297-304
The 31P NMR spectra of C6H5XCr(CO)2P(C6H5)3 (X = H, CH3, OCH3, N(CH3)2, COOCH3) (I), p-C6H4X2Cr(CO)2P(C6H5)3 (X = COOCH3)(II) and C6H3X3Cr(CO)2P(C6H5)3 (X = CH3) (III) complexes in neutral and acidic media were investigated. The protonation of complexes I and III in trifluoroacetic acid results in the greater upfield shielding of 31P{1H} signal. In this case the complexes I (X = H, CH3, OCH3) are completely protonated at the metal, complex I (X = COOCH3)is partially protonated, while no protonation occurs in the case of complex II.Temperature-dependence of the 31P{1H} NMR spectra was investigated for complexes I (X = H, OCH3) in a 1/10 mixture of trifluoroacetic acid and toluene and for complexes I (X = COOCH3) and II in trifluoroacetic acid. The degree of protonation was found to increase with decreasing temperature. 相似文献
9.
Bernd Weinberger Guy Tanguy Hervé Des Abbayes 《Journal of organometallic chemistry》1985,280(1):C31-C33
The ylid adduct (CO)4FeCH2P(C6H5)3 (I) was rapidly produced (along with (CO)4FeP(C6H5)3) by introducing iron pentacarbonyl into the following phase transfer system under nitrogen: CH2Cl2/P(C6H5)3; H2O/NaOH 1 M, Bu4N+2, SO42? Production of I goes through the transient generation of the tetracarbonyl ferrate anion Fe(CO)42?, which reacts with the dichloromethane. 相似文献
10.
The cyclopentadienylcobalt(I) compounds C5H5Co(PMe3)P(OR)3 (R = Me, Et, Pri) and C5H5Co(C2H4)L (L = PMe3, P(OMe)3, CO) are prepared by ligand substitution starting from C5H5Co(PMe3)2 and C5H5Co(C2H4)2. Whereas the reaction of C5H5Co(PMe3)P(OMe)3 with CH2Br2 mainly gives [C5H5CoBr(PMe3)P(OMe)3]Br, the dihalogenocobalt(III) complexes C5H5CoX2(PMe3) (X = Br, I) are obtained from C5H5Co(CO)PMe3 and CH2X2. Treatment of C5H5Co(CO)PMe3 or C5H5Co(C2H4)PMe3 with CH2ClI at low temperatures produces a mixture of C5H5CoCH2Cl(PMe3)I and C5H5CoCl(PMe3)I, which can be separated due to their different solubilities. The same reaction in the presence of ligand L gives the carbenoidcobalt(III) compounds [C5H5CoCH2Cl(PMe3)L]PF6 in nearly quantitative yields. If NEt3 is used as the Lewis base, the ylide complexes [C5H5Co(CH2PMe3)(PMe3)X]PF6 (X = Br, I) are obtained. The PF6 salts of the dications [C5H5Co(CH2PMe3)(PMe3)L]2+ (L = PMe3, P(OMe)3, CNMe) and [C5H5Co(CH2PMe3)(P(OMe)3)2]2+ are prepared either from [C5H5Co(CH2PMe3)(PMe3)X]+ and L, or more directly from C5H5Co(CO)PMe3, CH2X2 and PMe3 or P(OMe)3, respectively. The synthesis of C5H5CoCH2OMe(PMe3)I is also described. 相似文献
11.
ortho-Substituted aryliridium(I) complexes of the type [Ir(RnC6H5-n)(CO)L2] (RnC6H5-n = 2-EtC6H4; 2,6-Et2C6H3; L = PPh3 PMePh2) have been prepared from [IrCl(CO)L2] and the corresponding aryllithiums. With the exception of trans-[Ir(2-EtC6H4)(CO)(PPh3)2] these compounds show cis, trans isomerism. After separation, the isomers have been studied by NMR (1H, 31P), IR, and UV-VIS spectroscopy. ab]Durch Umsetzung von [IrCl(CO)L2] (L = PPh3, PMePh2) mit den entsprechenden Lithiumarylen wurden ortho-substituierte Aryliridium(I)-Komplexe des Typs [Ir(Rn C6H5-n)(CO)L2] (RnC6H5?n = 2-EtC6H4; 2,6-Et2C6H3; 2-Et-6-MeC6H3) dargestellt. Mit Ausnahme von trans-[Ir(2-EtC6H4)(CO)(PPh3)2] zeigen diese Verbindungen die Erscheinung der cis,trans-Isomerie. Die Isomere wurden getrennt und mit Hilfe NMR- (1H, 31P), IR- und UV/VIS-spektroskopischer Methoden untersucht. 相似文献
12.
Irradiation of solutions of n5-C5H5W(CO)3R (R CH3n1-CH2C6H5) in cyclohexane at ca. 310490 nm leads to the formation of [n5-C5H5W(CO)3]2 and methane and of n5-C5H5W5(CO)2(n3-CH2C6H5) and some [n5-C5H5W(CO)3]2, respectively. When the irradiation is carried out in the presence of excess P(C6H5)3, the photoproducts are n5-C5H5W(CO)2[P(C6H5)3]CH3 (R CH3) and n5-C5H5W(CO)2(n3-CH2C6H5) and trace [n5-C5H5W(CO)3]2 (R n1-CH2C6H5). Photolysis of the n5-C5H5W(CO)3R in the presence of benzyl chloride affords n5-C5H5W(CO)3Cl (R CH3) and both n5-C5H5W(CO)2(n3-CH2C2H5) and n5-C5H5W(CO)3Cl (R n1-CH2C6H5), the relative amounts of the latter products depending on the quantity of added C6H5CH2Cl. Irradiation of n5-C5H5W(CO)3-CH3 in the presence of both P(C6h5)3 and C6H5CH2Cl affords n5-C5H5W(CO)2-[P(C6H5)3]CH3, but no n5-C5H5W(CO)3Cl. It is proposed that the primary photo-reaction in these transformations is dissociation of a CO group from n5-C5H5W-(CO)3R to generate n5-C5H5W(CO)2R, which can either combine with L to form a stable 18 electron complex, n5-C5H5W(CO)2(L)R (L CO, P(C5H5)3; LR n3-CH2C6H5), or lose the group R in a competing, apparently slower step. This proposal receives support from the observation that, light intensifies being equal, n5-C5H5W(CO)3CH3 undergoes a considerably faster photoconversion to [n5-C5H5W(CO)3]2 under argon than under carbon monoxide. 相似文献
13.
《Journal of organometallic chemistry》1986,299(2):169-178
The complex cations [C5H5Fe(CO)2L]BF4 (L = (C6H5)3−nP(NR2)n; n = 0−3 R = CH3, C2H5) have been obtained from the reaction of [C5H5Fe(CO)2THF]BF4 (I) with L. The reaction of I with E(NR2)3 (E = As, Sb; R= CH3) is also described. Spectroscopic investigations (IR, 1H, 13C and 31P NMR) indicate an increase in electron density on the iron center through increase of the number of P-bound NR2 groups. 相似文献
14.
The interaction of C5H5Fe(CO)2I with (+)-α-methylbenzyl isocyanide yields the diastereoisomeric pair (+)- and (−)-C5H5Fe(CO)[CN-CH(CH3)- (C6H5)]I. The two diastereoisomers can be separated on the basis of their different solubilities by repeated precipitation from methylene chloride/pentane. Excluding light the complexes are configurationally stable in the solid state as well as in solution. In daylight, however, the optical rotations decrease rapidly (photoracemisation). The ORD and CD spectra (+)- and (−)-C5H5Fe(CO)[CN-CH(CH3)(C6H5)]I show pronounced Cotton effects. 相似文献
15.
The reaction of stoichiometric MeLi with the 1:1 mixture of (?5‐C5H5)Fe(CO)2I/P(OR)3 (R = Me, Et, and Ph) at ?78°C changes the bonding mode between metal and ring from (?5‐C5H5) to (?4‐exo‐MeC5H5) and the oxidation state of metal from Fe(II) to Fe(O), the novel complexes (?4‐exo‐MeC5H5)Fe(CO)2P(C)R)3 being obtained in 45‐57% yields. The reaction of trace MeLi with the 1:1 mixture of (?5‐C5H5)Fe(CO)2I/P(OMe)3 at ?78°C results in 70% yield of the phosphonate complex (?5‐C5H5)Fe(CO)2P(O)(OMe)2 which is an Arbuzov‐like dealkylation product from the cationic intermediate [(?5‐C5H5)Fe(CO)2P(OMe)3+] and the iodide. The amines could assist the Arbuzov‐like dealkylation of [(?5‐C5H5)Fe(CO)2P(OMe)3+] [PF6?] where iron‐carbamoyl intermediates are likely involved in the case of primary amines. 相似文献
16.
The interaction of [Mo(CO)3bipy]2 with various monodentate ligands L (L = NH3, pyr, P(C6H5)3, P(C6H5)Cl2, CN?, SO2) yields, according to the reaction equation in ?Inhaltsübersicht”?, mixed tricarbonyl compounds Mo(CO)3bipyL by cleavage of the CO bridges of the dimeric starting carbonyl. Oxidation of [Mo(CO)3D]2 (D = bipy, phen) by means of iodine, partly in the presence of free bipy or phen, leads to the covalent and ionic, respectively, compound types [MoII(CO)3DI2]2, [MoI(CO)2DI]2, [MoII(CO)2D2I]I and [MoII(CO)2D2I]I3. 相似文献
17.
G.E. Herberich J. Hengesbach G. Huttner A. Frank U. Schubert 《Journal of organometallic chemistry》1983,246(2):141-149
The thermal reaction of 1-phenyl-4,5-dihydroborepin (I) with Mn2(CO)10 produces the triple-decked complex (OC)3Mn(μ-L)Mn(CO)3 (III) where L is 2-ethyl-1-phenylborole. The analogous system I/[(C5H5)Fe(CO)2]2 inter alia yields the triple-decked sandwich complex (C5H5)Fe(μ-L)Fe(C5H5) (VI) and the borabenzene derivative (C5H5)Fe(2-CH3C5H4BC6H5) (VIII). The structures of the 30-electron compounds III and VI have been determined by X-ray analyses. 相似文献
18.
The ligands L P(C2H5)3, P(C6H5)3, P(OCH3)3 and P(OC6H5)3 react with [Fe(CO)3(S-t-C4H9)]2 to give mono-substituted Fe2(CO)5L(S-t-C4H9)2 or bis-substituted [Fe(CO)2L(S-t-C4H9)]2 depending on the reaction conditions. With the exception of [Fe(CO)2P(C2H5)3(S-t-C4H9)]2, the latter derivatives occur both in solution and in the solid state as a single isomer in which the ligands L are bonded trans to the metal-metal bond. Whereas an asymmetrically bis-substituted product, Fe(CO)3(S-t-C4H9)2Fe(CO)L' is formed in the reaction of [Fe(CO)3(S-t-C4H9)]2 with L' &2.dbnd; cis-(C6H5)2PC2H2P(C6H5)2, symmetrically bis-substituted derivatives [Fe(CO)2(S-t-C4H9)]2L', in which the ligand bridges the two iron atoms are produced in the corresponding reactions involving L' (C6H5)2P(CH2nP(C6H5)2 (n 1 and 2). The NMR spectrum of [Fe(CO)2P(OCH3)3(S-t-C4H9)]2, as well as those of the complexes [Fe(CO)2P(OCH3)3SR]2 (R CH3 and i-C3H7) which have also been synthesised in this study, is interpreted in terms of a virtual coupling effect. 相似文献
19.
P. Jaitner 《Journal of organometallic chemistry》1982,231(3):225-227
The photoinduced synthesis and spectroscopic properties of the new mixed metal compound [Mn3Re(CO)12(SC6H5)4] by UV irradiation of a mixture of Mn2(CO)10, Re2(CO)10 with S2(C6H5)2 is described. No mixed sulphur/selenium compounds [M4(CO)12SnSe4?n(C6H5)4] (M = Mn or Re, n = 1–3) could be obtained by analogous photoreactions. 相似文献
20.
M.G. Peterleitner M.V. Tolstaya V.V. Krivykh L.I. Denisovitch M.I. Rybinskaya 《Journal of organometallic chemistry》1983,254(3):313-315
Electrochemical oxidation of (η-1,3,5-Me3C6H3)Cr(CO)3 in the presence of P(OEt)3 with subsequent electrochemical reduction results in the formation of a (η-1,3,5-Me3C6H3)Cr(CO)2[P(OEt)3] and (η-1,3,5-Me3C6H3)Cr(CO)[P(OEt)3]2 mixture. Under similar conditions (η6-arene)Cr(CO)3, where arene = 3,5-Me2C6H3(CH2)2OPR2 (R = OEt,OPh,F), yields the corresponding arenephosphite chelate complexes. 相似文献