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1.
Perfluoromethyl Element Ligands. XLIII [1] Novel Synthetic Routes to Binuclear Complexes of the Type MM′(CO)8ER2X (M/M′ = Mn/Mn, Mn/Re, Re/Re; E = P, As; R = CF3, Me; X = Hal, ) Mn(CO)5I reacts with compounds of the type (CF3)2EAsMe2 (E = P, As) as with the symmetric E2(CF3)4 ligands in the first step with cleavage of the E‐As bond to yield the pro ducts (CO)5MnE(CF3)2 and Me2AsI. Reaction of the mononuclear complexes with excess of Mn(CO)5I leads in good yields to the known dinuclear compounds (CO)4Mn[E(CF3)2, I]Mn(CO)4 and CO. Me2AsI, the second product of the EAs cleavage, attacks the starting compound Mn(CO)5I giving cis‐Mn(CO)4I(AsMe2I) and CO. This result encouraged us to thoroughly investigate the preparation of cis‐M(CO)4X(EMe2Y) complexes with most of the possible combinations of M = Mn, Re; E = P, As and X, Y = Cl, Br, I. An alternative route to these compounds was opened by the cleavage of the dinuclear manganese or rhenium halides M2(CO)8X2 with the halophosphanes or ‐arsanes Me2EY. This route was found to be especially advantageous for the preparation of the rheniumcarbonyl precursors, since milder conditions than for the CO‐substitution in Re(CO)5X compounds are sufficient for the halogen‐bridged dinuclear complexes. Cis‐M(CO)4X(EMe2Y) complexes were used as precursors for the synthesis of novel homo‐ and heterodinuclear complexes of the type (CO)4M(EMe2, X)M′(CO)4 by reacting the EY function with transition metal carbonylates Kat[M′(CO)5] (Kat = Na, Bu4N, Ph4As). Thus the preparation of a wide range of complexes was possible, which before had been successfully prepared by the direct reaction of Mn2(CO)10 with Me2EX only in few cases, e. g. with Me2AsI. Spectroscopic investigations, using the CO valence frequencies and the 1H‐NMR data of the ligands EMe2Y or of the Me2E bridges, were applied to study the influence of the variables M, M′, E, X, Y and Kat on the reactivity of the mononuclear complexes and the bonding situation in both the mono‐ and the dinuclear systems. The new compounds were characterized by spectroscopic (IR, NMR, MS) and analytic methods (C, H). 相似文献
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The reactions of M(CO)5X ( M = Mn, Re; X = Cl, Br, I) with E2(CF3)4 (E = P, As) between 50 and 90°C yield binuclear complexes of the type M2(CO)8E(CF3)2X with two different bridging ligands, the formation of which is influenced by M (Mn > Re), E (P > As) , and X(I > Br > Cl). The main by-product is the symmetrical system M2(CO)8[E(CF3)2]2, which is however not formed by the partial replacement of X by E(CF3)2 since this reaction requires temperatures above 120°C. The observed products can be explained by a three-step reaction path starting with the cleavage of E2(CF3)4 followed by the subtitution of a cis-CO group in the M(CO)5X component by M(CO)5E(CF3)2 and the ring closure. 相似文献
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Transition Metal-substituted Acylphosphanes and Phosphaalkenes. 22. Insertions of Hexafluoroacetone into the PX-Bond of Metallophosphanes (η5-C5Me5)(CO)2M? PX2 (M = Fe, Ru; X = Me3Si, Cl). Structure Determination of (η5-C5Me5)(CO)2Fe? P(SiMe3)C(CF3)2(OSiMe3) Reaction of the metallophosphanes (η5-C5Me5)(CO)2M? P(SiMe3)2 ( 1a : M = Fe; 1b : M = Ru) with hexafluoroacetone (HFA) afforded the complexes (η5-C5Me5)(CO)2M? P(SiMe3)C(CF3)2(OSiMe3) ( 2a, b ). The attempted synthesis of a metallophosphaalkene from 2a by thermal elimination of hexamethyldisiloxane failed. The acid catalyzed hydrolysis of 2a afforded compound (η5-C5Me5) · (CO)2Fe? P(H)C(CF3)2(OSiMe3) ( 3 ). Hexafluoracetone and (η5-C5Me5)(CO)2Fe? PCl2 ( 4 ) under-went reaction to give the metallochlorophosphan (η5-C5Me5) · (CO)2Fe? P(Cl)? O? C(CF3)2Cl ( 5 ). Constitutions and configurations of the compounds ( 2–5 ) were established by elemental analyses and spectroscopic data (IR, 1H-, 13C, 19F-, 29Si-, 31P-NMR, MS). The molecular structure of 2a was determined by x-ray diffraction analysis. 相似文献
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Alternative Ligands. XXVI. M(CO)4 L-Complexes (M ? Cr, Mo, W) of the Chelating Ligands Me2ESiMe2(CH2)2E′ Me2 (Me ? CH3; E ? P, As; E′ ? N, P, As) The reaction of M(CO)4NBD (NBD = norbornadiene; M ? Cr, Mo, W) with the ligands Me2ESiMe2(CH2)2E′ Me2 yields the chelate complexes (CO)4M[Me2ESiMe2]) for E,E′ ? P, As, but not for E and /or E′ ? N. The NSi group is not suited for coordination because of strong (p-d)π-interaction. In the case of the ligands with E ? P or As and E′ ? N chelate complexes can be detected in the reaction mixture, but isolable products are complexes with two ligands coordinated via the E donor group. The new compounds are characterized by analytical and spectroscopic (IR, NMR, MS) investigations. The spectroscopic data are also used to deduce the coordinating properties of the ligands. X-ray diffraction studies of the molybdenum complexes (CO)4Mo[Me2ESiMe2(CH2)2AsMe 2] (E ? P, As) in accord with the observed coordination effects show only small differences between SiE and CE donor functions. Attempts to use the ligands Me2ESiMe2(CH2)2AsMe2 (E ? P, As) for the preparation of Fe(CO)3L complexes result in the fission of the SiE bonds and the formation of the binuclear systems Fe2(CO)6(EMe2)2 (E ? P, As) together with the disilane derivative [Me2Si(CH2)2AsMe2]2. 相似文献
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Perfluoromethyl-Element-Ligands. XVIII. Preparation and Spectroscopic Investigation of M(CO)5L and M(CO)4L2 Complexes [L = MenP(CF3)3?n; n = 0–3; M = Cr, Mo, W] M(CO)5L and cis-M(CO)4L2 complexes, respectively [M = Cr, Mo, W; L = MenP(CF3)3?n; n = 0–3] are prepared reacting M(CO)5 · THF or M(CO)4norbor with L at room temperature. The cis-compounds isomerize above 50°C yielding the trans-complexes; the rate of isomerization increases with increasing number of CF3 groups. Thermal reaction of M(CO)6 (M = Cr, Mo, W) with P(CF3)3 yields M(CO)5P(CF3)3 and trans-M(CO)4[P(CF3)3]2. Introduction of three P(CF3)3 ligands by reaction with M(CO)3(cycloheptatriene) (M = Cr, Mo) proves unsuccessful; besides little M(CO)5P(CF3)3 trans-M(CO)4[P(CF3)3]2 is formed. The new compounds are characterized by analytical and spectroscopic (n.m.r., i.r., MS) methods. 相似文献
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Perfluoromethyl-Element-Ligands. XXXV. Reactivity of Metallated Phosphanes and Arsanes of the Type π-C5H5(CO)3MER2 (M ? Cr, Mo, W; E ? P, As; R ? CF3, CN) The influence of the complex fragments π-C5H5(CO)3M (M ? Cr, Mo, W) on the basicity of the metallated phosphanes or arsanes π-C5H5(CO)3MER2 (E ? P, As; R ? CF3, CN) has been investigated by reactions with sulfur, methyliodide, fluorotrichloromethane, and W(CO)5THF, respectively. π-C5H5(CO)3ME(CF3)2 (E ? P: 1a–c ; E ? As: 2a–c ) react with sulfur only for E ? P to give the complexes π-C5H5(CO)3P(S)(CF3)2 ( 5a–c ) in good yield. The attempted thermal transformation of the phosphane sulfides to η2 coordinated (CF3)2P?S complexes proves unsuccessful. The reactions of 1a–c, 2a–c and π-C5H5(CO)3MP(CN)2 ( 3a–c ) with CH3I or CCl3F do not lead to onium salts, but to cleavage of the M–E bonds forming π-C5H5(CO)3MX (X ? I, Cl) and CH3ER2 and R2ECCl2F, respectively. The reactivity depends on ER2 and M: P(CF3)2 > P(CN)2 > As(CF3)2; Cr > Mo > W. Due to the low donor ability of the complexes 1a–c, 2a–c and 3a–c binuclear compounds π-C5H5(CO)3MER2W(CO)5 (E ? As, R ? CF3: 11a–c ; E ? P, R ? CN: 12a–c ; ER2?P(CN)Ph: 13a, b ) are obtained only with the highly reactive W(CO)5THF. In case of the (CF3)2P bridged derivatives spontaneous CO-elimination leads to the threemembered ring systems ( 10a–c ). 相似文献
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Perfluoromethyl Element Ligands. XXX. Reactions of the Metal Hydridesπ-C5H5(CO)3MH (M = Cr, Mo, W) with Organoelement-Element Compounds of the Type R2 EER2 and RE′ ′E ′R (E = P, As; E′ = S, Se; R = CH3, CF3) Cleavage reactions of R2EER2 and RE′E′R, respectively, (E = P, As; E′ = S, Se; R = CH3, CF3) with complexes π-C5H5(CO)3MH (M = Cr, Mo, W) are used (a) to prepare known and novel complex subsituted phosphanes, arsanes, sulfanes, or selanes π-C5H5(CO)3MER2 (I) and π-C5H5(CO)3ME′R (II), respectively, (b) to study the reactivity trends as a function of E, E′, R, and M (see Inhaltsübersicht). The tendency observed for the formation of the binuclear complexes [π-C5H5(CO)2MER2]2 and [π-C5H5(CO)2ME′R]2, respectively, in following reactions of I and II increases in the series W ? Mo ≤ Cr and SeCF3 < As(CF3)2 < SCF3 ≈ P(CF3)2 < SeMe < AsMe2 ?; PMe2 ≈ SMe. 相似文献
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The reaction of Re2(CO)10 with E2(CF3)4 (E = P, As) yields the binuclear complexes Re2(CO)8[E(CF3)2]2 with two E(CF3)2 bridges. The complexes Re2(CO)8E(CF3)2I (E = P, As) and Re2(CO)8As(CF3)2Cl, containing two different bridges, are formed in the reactions of Re2(CO)10 with (CF3)2EI (E = P, As) and (CF3)2AsCl, respectively. A series of new binuclear complexes is obtained on substitution of iodine in the compounds Re2(CO)8E(CF3)2I (E = P, As) by SCH3, SCF3, SeCF3, P(CH3)2 and H. The binuclear complexes Re2(CO)8(E′CF3)2 having two E′CF3 bridges (E′ = S, Se) are obtained reacting Re(CO)5I With Hg(E′CF3)2. At room temperature the mononuclear complex Re(CO)5SeCF3 is obtained. Substitution of iodine in Re2(CO)8I2 by SCF3 also yields the symmetrical compound Re2(CO)8(SCF3)2; reduction with NaBH4 gives the binuclear hydride Re2(CO)8HJ. - IR and NMR spectra (1H, 19F) of the new complexes are reported and discussed. 相似文献
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W(CO)5L complexes (L = R2EER′2, R2EE′R; R, R′ = CH3, CF3; E = P, As; E′ = S, Se, Te) have been prepared by reaction of W(CO)5·THF with L at room temperature or by redistribution reaction of W(CO)5E2Me4 with E2(CF3)4 or E′2Me2 as well as by cleavage of E2(CF3)4 with W(CO)5EMe2H. The new compounds were characterized by analytical and spectroscopic (IR, NMR, MS) methods; by comparison with of the data of free and coordinated ligands the effects of complexation are studied. 相似文献
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The insertion of (CF3)2CO into the PH bond of MenH3?nP yields MenH2?nPC(CF3)2OH and MenH1?nP[C(CF3)2OH]2 (n=O, 1), respectively [1]. MeP[C(CF3)2OH]2 rearranges giving the diphosphine [MePOCH(CF3)2]2 and the phosphorane MeP[OCH(CF3)2]4. Me2PH reacts with (CF3)2CO forming several products, e.g. MePF[OCH(CF3)2]2 and Me2PPMe2 [1]. The phosphines tBu(R)PH(R=Me, tBu), however, add (CF3)2CO giving rise to the phosphinites tBu(R)POCH(CF3)2, which furnish stable phosphonium salts upon treating with MeI. (CF3)2CO inserts into the SH bond of RSH to yield RSC(CF3)2OH (R=H,Me,Ph), which were reacted with MeI, too. Reacting SCl2 with LiOCH(CF3)2 gives S[OCH(CF3)2]2 which is oxidised by chlorine to the sulfurane ClS[OCH(CF3)2]3 [2]. The sulfurane is able to transfer (CF3)2CHO groups to phosphorus (III) compounds, e.g. P[OCH(CF3)2]3 and Me3P yielding P[OCH(CF3)2]5 and [Me3POCH(CF3)2]+Cl?. ClS[OCH(CF3)2]3 gives a stable salt upon reaction with SbCl5, like ClP[OCH(CF3)2]4. The mechanisms for these reactions are discussed. 相似文献
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Heteronuclear Metal Atom Clusters of the Types X4?n[SnM(CO)4P(C6H5)3]n and M2(CO)8[μ-Sn(X)M(CO)4P(C6H5)3]2 by Reaction of SnX2 with M2(CO)8[P(C6H5)3]2 (X = Halogene; M = Mn, Re; n = 2, 3) The compounds of the both types X4?n[SnM(CO)4P(C6H5)3]n (n = 3; M = Mn; X = F, Cl, Br, I. n = 2: M = Mn, Re; X = Cl, Br, I) and M2(CO)8[μ-Sn(X)M(CO)4P(C6H5)3]2 (M = Mn; X = Cl, I. M = Re; X = Cl, Br, I) are prepared by reaction of SnX2 with M2(CO)8[P(C6H5)3]2 (M = Mn, Re). Their IR frequencies are assigned. In Re2(CO)8[μ-Sn(Cl)Re(CO)4P(C6H5)3]2 the central molecule fragment contains a planar Re2Sn2 rhombus with a transannular Re? Re bond of 316.0(2) pm. Each of the SnIV atoms is connected with the terminal ligands Cl and Re(CO)4P(C6H5)3. These ligands are in transposition with respect to the Re2Sn2 ring. The mean values for the remaining bond distances (pm) are: Sn? Re = 274.0(3); Sn? Cl = 243(1), Re? C = 176(5), Re? P = 242.4(9), C? O = 123(5). The factors with an influence on the geometrical shape of such M2Sn2 rings (M = transition metal) are discussed. 相似文献
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Transition Metal Phosphido Complexes. XIII. P-functional Phosphido-Bridged Heterobimetallic Complexes with and without a Metal-Metal Bond; P(SiMe3)2-Bridged cp(CO)xFe Derivatives cp(CO)2FeP(SiMe3)2 1 reacts with the carbonyl nitrosyl complexes Co(CO)3(NO), Fe(CO)2(NO)2,Mn(CO)(NO)3 substituting a CO ligand and with the THF complexes M′(CO)5THF(M′ = Cr, Mo, W), Mncp(CO)2THF MnMecp(CO)2 which can be obtained in solution substituting the THF ligand to give the phosphido-bridged bimetallic complexes cp(CO)2Fe[μ-P(SiMe3)2]M′Lm 2 (M′Lm = Co(CO)2(NO) b , Fe(CO)(NO)2 c , Mn(NO)3 d , Cr(CO)5 f , Mo(CO)5 g , W(CO)5 h , Mncp(CO)2 i , MnMecp(CO)2 j ). Solutions of Li(Me3Si)2PM′Lm 4e–l (M′Lm = Fe(CO)4 e , Crcp(CO)(NO) k , Vcp(CO)3 l ) are available by a selective cleavage reaction of a Si? P bond in the complexes (Me3Si)3PM′Lm 3e–l using n-BuLi. Reactions of cp(CO)2FeBr with 4e–l give the bimetallic complexes 2e–l . The open-chain complexes 2c, 2f, 2h–k undergo a photochemical decarbonylation reaction to form the phosphido-bridged bimetallic complexes cp(CO)Fe[μ-CO, μ-P(SiMe3)2]M′Lm?1(Fe-M′) 5 (M′Lm?1 = Fe(NO)2 c , Cr(CO)4 f , W(CO)4 h , Mncp(CO) i , MnMecp(CO) j , Crcp(NO) k ) containing a metal-metal bond. Equilibria between various isomers can partially be observed in solutions of the complexes 5. I.R., N.M.R., and mass spectral data are reported. 相似文献
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Perfluoromethyl Element Ligands. XLII Binuclear Complexes of the Type Mn2(CO)8E(CF3)2E′R (E = P, As; E′ = S, Se, Te): Synthesis and Structure Complexes of the type Mn2(CO)8E(CF3)2E′R, in which the groups E(CF3)2 and E′R act as bridging ligands, are prepared either by direct reactions of Mn2(CO)10 with (F3C)2EE′R (E = P, As; E′ = S, Se, Te) or by substitution of the iodine bridge in the representatives Mn2(CO)8 E(CF3)2I (E = P, As) with mercury compounds Hg(E′R)2. As a rule the binuclear systems contain four‐membered heterocycles (Mn2EE′). However, the reactions of Mn2(CO)10 with (F3C)2PE′P(CF3)2 (E′ = S, Se) yield five‐membered rings [Mn2P(E′P)]. The compounds have been characterized by spectroscopic (NMR, IR, MS), analytic (C, H) and X‐ray diffraction investigations. The pyramidal Mn2E′R fragment shows dynamic behaviour in solution via inversion between two identical structures. 相似文献
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Phosphido- and Arsenido-bridged Dinuclear Complexes. Synthesis and Molecular Structure of (η5-C5H4R)2Zr{μ-P(SiMe3)2}2M(CO)4 (R = Me, M = Cr; R = H, M = Mo) and Synthesis of (η5-C5H5)2Zr{μ-As(SiMe3)2}2Cr(CO)4 The reaction of (η5-C5H4R)2Zr{E(SiMe3)2}2 with M(CO)4(NBD) (NBD = norbornadiene) yields the dinuclear phosphido- or arsenido-bridged complexes (η5-C5H4R)2Zr{μ-E(SiMe3)2}2M(CO)4 (R = Me, E = P, M = Cr ( 1 ); R = H, E = P, M = Mo ( 2 ); R = H, E = As, M = Cr ( 3 )). No formation of dinuclear complexes was observed in the reaction of (η5-C5H4Me)2Zr{P(SiMe3)2}2 with Ni(PEt3)4, Ni(CO)2(PPh3)2 or with NiCl2(PPh3)2 in the presence of Mg. Complexes 1 – 3 were characterised spectroscopically (i. r., n. m. r., m. s.), and X-ray structure investigations were carried out on 1 and 2 . The central four-membered ZrP2M ring is slightly puckered (dihedral angle between planes ZrP2/CrP2 14.7°, ZrP2/MoP2 14.2°). The Zr? P bond lengths are equivalent ( 1 : Zr? P1 2.654(4), Zr? P2 2.657(4) Å; 2 : Zr? P1 2.6711(9), Zr? P2 2.6585(7) Å), as are the M? P bond lengths (M = Cr ( 1 ): Cr? P1 2.513(4), Cr? P2 2.502(4) Å; M = Mo ( 2 ): Mo? P1 2.6263(7), Mo? P2 2.6311(10) Å). The long Zr ··· M distances of 3.414 Å (M = Cr ( 1 )) and 3.461 Å (M = Mo ( 2 )) indicate the absence of a metal-metal bond. 相似文献
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Perfluoromethyl Element Ligands. XXIX. Preparation and Spectroscopic Investigation of M(CO)4L2 Complexes (M ? Cr, Mo, W; L ? Me2PSMe, Me2PSeMe, (CF3)2PSMe, (CF3)2PSMe) The complexes M(CO)4L2 (see Inhaltsübersicht) have been prepared by the reaction of tetracarbonyl norbornadiene metal compounds M(CO)4NBD with L at room temperature or 35°C, respectively. The cis-complexes formed in the first step undergo rearrangement to trans-isomers at higher temperatures. New compounds have been characterized by analytical and spectroscopic (IR, NMR, MS) methods. 相似文献
19.
Wolfgang A. Herrmann Erdmuthe Voss Ernst Guggolz Manfred L. Ziegler 《Journal of organometallic chemistry》1985,284(1):47-57
Upon treatment of the labile ether complex (η5-C5Me5)Mn(CO)2(THF) (1) with monosilane the novel dinuclear complex of composition (μ-SiH2)[(η5-C5Me5)Mn(CO)2H]2 (2) is formed in 15% isolated yield via double oxidative addition of the binary hydride precursor. According to a single-crystal X-ray diffraction study, the molecule exhibits a bent MnSiMn′ framework (≮Mn, Si, Mn′ 124.4(3)°), with the manganese—silicon bond lengths representing single bonds (243.4(3) pm). The resulting distance of 430.6 pm between the manganese atoms precludes any metal—metal bonding so that the complex fragments (η5-C5Me5)Mn(CO)2H are exclusively connected to each other via the bridging silylene ligand. The hydrogen ligands attached to the manganese atoms could not be located by X-ray diffraction methods but were detected by NMR spectroscopy (δ(SiH) 4.59, δ(MnH) ?11.55; CDCl3). Although thermolysis of 2 yields elemental hydrogen, the expected and hitherto unknown complex (μ-Si)[(η5-C5Me5)Mn(CO)2]2 is not observed. 相似文献
20.
Roman Maisch Martina Barth Wolfgang Malisch 《Journal of organometallic chemistry》1984,260(2):C35-C39
Metallation of PCl3 with Na[M(CO)3C5Me5] (M Mo, W) (1a, 1b) yields the metallodichlorophosphanes C5Me5(CO)3MPCl2 (2a, 2b), which show a remarkable thermal stability due to metal—phosphorus bond strengthening by the electron-donating C5Me5 group. Treatment of 2a with Me3P leads to the formation of C5Me5(CO)2(Me3P)MoCl (4) via CO/Me3P-exchange at 2a and subsequent elemination of “PCl”. The high Lewis basicity of 2a, 2b, which has to be referred to the high electron donor capacity of the transition metal unit is proved by the spontaneous reaction with elemental sulfur or BH3 · THF to give the mtallodichlorophosphine sulfide C5Me5(CO)3MPCl2(S) (5a, 5b) or the borane adducts C5Me5(CO)3MPCl2BH3 (6a, 6b), respectively. The new metal-phosphorus compounds are characterized by IR and NMR spectroscopy. 相似文献