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1.
Carbonyl Monoolefin Derivatives of the Group VI Transition Metals. I. Tetracarbonyl Phosphine Olefin Complexes Monoolefin complexes cis-M(CO)4(PR3)(olefin) (M ? Cr, Mo, W; R ? Et, Bu, Pri, Ph; olefin ? maleic anhydride, dimethyl maleate, dimethyl fumarate, bis(trimethylsilyl) fumarate, ethylene) are obtained from the ionic compounds Et4N[R3PM(CO)4Cl] either via ethanol or acetonitrile derivatives M(CO)4(PR3)L, or directly in a two phase system. The olefins are displaced by Lewis-bases such as amines or phosphines under mild conditions. 相似文献
2.
Transition Metal Phosphido Complexes. XIV. P-Functional Phosphido-Bridged Heterobimetallic Complexes with and without a Metal-Metal Bond; PH2-Bridged cp(CO)xFe-Derivatives Cleaving both Si? P bonds in the complexes cp(CO)2[μ-P(SiMe3)2]M′Lm 1 (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 , Crcp(CO)(NO) k , Vcp(CO)3 l ) using CH3OH, H2O or CH3COOH, respectively, gives the PH2-bridged bimetallic complexes cp(CO)2Fe(μ-PH2)M′Lm 2b – d and 2f – l . The complexes H3PM′Lm 4e, 4f, 4j (M′Lm = Fe(CO)4 e ) which can be obtained reacting the P-silylated derivatives (Me3Si)3PM′Lm with CH3OH can be transformed into LiH2PM′Lm 5e, 5f, 5j using n-BuLi. 5e, 5f, 5j react with cp(CO)2 FeBr to give 2e, 2f, 2j . The photochemical decarbonylation of 2b - l leads only in the case of 2i and 2j to isolable complexes containing a metal-metal bond cp(CO)Fe(μ-CO, μ-PH2) M′Lm?1 6 (M′Lm?1 = Mncp(CO) i , MnMecp(CO) j ). 6i and 6j as well as 6k (M′Lm?1 = Crcp(NO) k ) are also available cleaving both Si? P bonds in cp(CO)Fe[μ-CO, μ-P(SiMe3)2]M′Lm?1 8i – k using CH3OH. In other complexes 6 the PH2-bridge causes a labilisation of the metal-metal bond. This can be used in some cases to add ligands under mild conditions. I.R., N.M.R. and mass spectral data are reported. 相似文献
3.
Phosphine Substituted Chelate Ligands. XVIII. Penta- and Tetracarbonylmetal Complexes of Chromium, Molybdenum, and Tungsten with Secondary and Tertiary Phosphinothioformamide Ligands Mono- and bidentately coordinated phosphinothioformamide complexes are obtained by photochemical substitution of the metal hexacarbonyls M(CO)6 (M ? Cr ( a ), Mo ( b ), W ( c )). The M(CO)5 · THF adducts react with secondary thioamides under exclusion of light to give the P-coordinate pentacarbonyl complexes [(CO)5MPPh2C(S)NHR1] (R1 ? Ph ( 1a – c ), Me ( 2a )). The photoreaction of M(CO)5 · THF with secondary and tertiary thioamides at low temperatures leads to the formation of the P, S-chelate complexes . The corresponding N-silylated complexes 6a – c (R1 ? Me3Si, R2 ? Ph) are obtained by direct photosubstitution of M(CO)6 in cyclohexane solution. The labile bis(thioformamide) complexes [(CO)4M(PPh2C(S)NHMe)2] ( 7a – c , cis-trans isomers) are synthesized in low yields according to the same procedure. The attempted alkylation of the chelate complexes 3a – c remains unsuccessful, whereas the secondary thioformamides react with n-BuLi/CH2Br2 to give the methylene bis(thioformirnidoesters) [Ph2PC(NR1)S]2CH2 (R1 ? Ph (8), Me ( 9 )) in quantitative yields. 相似文献
4.
Tungsten Complexes of Diphosphanylacetylenes Diphosphanylacetylenes, R2P? C?C? PR2 [R?N(C2H5)2 ( 1 ), N[(CH2)2]2O ( 2 ), OCH3 ( 3 )] and W(CO)5 · tetrahydrofurane form the mononuclear complexes R2P? C?C? PR2 · W(CO)5 [R?N(C2H5)2 ( 1a ), N[(CH2)2]2O ( 2a )], the dinuclear complexes (CO)5W? PR2? C?C? PR2? W(CO)5 [R?N(C2H5)2 ( 1b ), N[(CH2)2]2O ( 2b ), OCH3 ( 3b )], and the trinuclear complex (CO)5W? PR2? C?C? PR2? W(CO)4? PR2? C?C? PR2? W(CO)5 [R?N(C2H5)2 ( 4 )]. The new compounds are characterized by their NMR, mass, and IR spectra. The results of an X-ray structural analysis of 4 are reported. 相似文献
5.
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
6.
Metal Complexes with Anionic Ligands of Elements of the Main Group IV. VII(1) Substitution Reactions of Carbonylnitrosyl and Nitrosyltrifluorophosphine Transition Metal Complexes with Trichlorostannid L-substitution by [SnCl3]? occurs if the nitrosyl complexes Co(NO)L3 and Fe(NO)2L2 (L = CO or PF3) are reacted with [N(C2H5)4][SnCl3] thermically in tetrahydrofuran as well as photochemically induced in methylenechloride. The complexes Co(NO)L3 yield the mono-substitution products [N(C2H5)4][Co(NO)L2SnCl3], with the iron compounds Fe(NO)2L2 only the disubstituted derivative [N(C2H5)4]2[Fe(NO)2(SnCl3)2] can be isolated. On the other hand CO substitution at (π-C5H5)Mo(NO)(CO)2 by UV irradiation did not suceed both with [SnCl3]? and with PF3. From the IR-spectroscopic data a leastly with PCl3 comparable π-acceptor ability is derived for the trichlorostannido ligand. 相似文献
7.
The photochemistry of the tris-substituted clusters Ru3(CO)9(PR3)3 (R=Ph or OMe) with no added ligands, with CO, C2H4, alkynes and H2 is compared and contrasted with results obtained for analogous thermal reactions. Photolysis of a CH2Cl2 solution of Ru3(CO)9(PPh3)3 leads to the metallated complex HRu3(CO)8(PPh3)2(PPh2C6H4). In CCl4, Ru(CO)3(PR3)Cl2 is formed on photolysis of Ru3(CO)9(PR3)3. Photolysis of CO saturated solutions of Ru3(CO)9(PR3)3 leads to Ru(CO)4(PR3). C2H4 saturated solutions of Ru3(CO)9(PR3)3 generate the novel Ru(CO)3(PR3)(2-C2H4) complexes upon photolysis. With C2H2, photolysis of solutions of Ru3(CO)9(PR3)3 leads to the novel complexes Ru(CO)3(PR3)(2-C2H2). Substituted alkyne complexes have been prepared. Thermolysis of Ru3(CO)9(PR3)3 with HCCPh leads to the novel acetylide clusters HRu3(CO)6(PR3)3(3-2-C2Ph). With PhC CPh, only Ru3(CO)9{P(OMe)3}3 reacts, yielding the novel alkyne cluster Ru3(CO)6{P(OMe)3}3(3-2-C2Ph2). With H2, photolysis of CH2Cl2 solutions of Ru3(CO)9(PR3)3 leads to H2Ru(CO)2(PR3)2. Irradiating a 4:1 CH2Cl2 to EtOAc solution of Ru3(CO)9(PR3)3 under an atmosphere of H2 leads to the novel dihydrido species H2Ru3(CO)7(PR3)3. Thermolysis of H2 saturated solutions of Ru3(CO)9(PR3)3 leads to H4Ru4(CO)8(PR3)4. 相似文献
8.
Sulfur Dioxide as Ligand and Synthon. IX. Reactions of Cobalt Carbonyls with Sulfur Dioxide – Synthesis and Characterization of Alkoxysulfinyl-Cobalt Carbonyl Complexes Reactions of phosphine substituted Co2(CO)8, (Ph2P–(CH2)n–PPh2: n = 1, dppm; n = 2, dppe; n = 3, dppp; n = 4, dppb), alkylcobalt carbonyls and alkoxycobalt carbonyls with sulfur dioxide have been investigated. The SO2 containing cobalt complexes are characterized by means of I.R., 1H-NMR, and mass spectra. Further on synthesis and properties of new alkoxysulfinylphosphine-cobalttricarbonyl complexes of the type ROS(O)Co(CO)3PR31 (R = Ph3Si, Me; R1 = Et, i-Pr, Ph) are described. 相似文献
9.
William Levason Luke P. Ollivere Gillian Reid Nikolaos Tsoureas Michael Webster 《Journal of organometallic chemistry》2009,694(15):2299-8506
A range of complexes of the binucleating tetrathio- and tetraseleno-ether ligands, 1,2,4,5-C6H2(CH2EMe)4 (E = S, L3 or Se, L4) or C(CH2EMe)4 (E = S, L5 or Se, L6) and of bidentate analogues 1,2-C6H2(CH2EMe)2 (E = S, L1 or Se = L2) with molybdenum and tungsten carbonyls and manganese carbonyl chloride have been prepared, and characterised by IR and multinuclear NMR (1H, 13C{1H}, 77Se, 55Mn, 95Mo) spectroscopy and mass spectrometry. Crystal structures are reported for [Mo(CO)4(L2)], [Mo(CO)4(L3)], [Mo(CO)4(μ-L3)Mo(CO)4], [Mo(CO)4(L4)], [Mn(CO)3Cl(μ-L3)Mn(CO)3Cl], [Mo(CO)4(μ-L5)Mo(CO)4], [Mn(CO)3Cl(L5)] and two forms (containing meso and DL diastereoisomers) of [W(CO)4(L5)]. 相似文献
10.
Marta S. Saraiva Susana Quintal Fátima C.M. Portugal Telma A. Lopes Vitor Félix José M.F. Nogueira Margarida Meireles Michael G.B. Drew Maria José Calhorda 《Journal of organometallic chemistry》2008,693(21-22):3411-3418
Reactions of [Mo(η3-C3H5)Br(CO)2(NCMe)2] with the bidentate nitrogen ligands 2-(2′-pyridyl)imidazole (L1), 2-(2′-pyridyl)benzimidazole (L2), N,N′-bis(2′-pyridinecarboxamido)-1,2-ethane (L3), and 2,2′-bisimidazole (L4) led to the new complexes [Mo(η3-C3H5)Br(CO)2(L)] (L = L1, 1; L2, 2; L4, 4) and [{Mo(η3-C3H5)Br(CO)2}2(μ-L3)] (3).The reaction of complexes 2 and 3 with Tl[CF3SO3] afforded [Mo(η3-C3H5)(CF3SO3)(CO)2(L2)] (2T) and [{Mo(η3-C3H5)(CF3SO3)(CO)2}2(μ-L3)] (3T).Complexes 3 and 2T were structurally characterized by single crystal X-ray diffraction, showing the facial allyl/carbonyls arrangement and the formation of the axial isomer. In 2T, two molecules are assembled in a hydrogen bond dimer.The four complexes 1–4 were tested as precursors in the catalytic epoxidation of cyclooctene and styrene, in the presence of t-butylhydroperoxide (TBHP), with moderate conversions and turnover frequencies for complexes 1–3 and very low ones for 4. The increasing number of N–H groups in the complexes seems to be responsible for the loss of catalytic activity, compared with other related systems. The cytotoxic activities of all the complexes were evaluated against HeLa cells. The results showed that compounds 1, 2, 4, and 2T exhibited significant activity, complexes 2 and 2T being particularly promising. 相似文献
11.
Reactions of monooxidized thioyl and selenoyl bis(phosphanyl)amine ligands C10H7‐1‐N(P(E)Ph2)(PPh2) [E = S ( 1 ), Se ( 2 )] with Mo(CO)4(pip)2 and W(CO)4(cod) afforded the complexes [M(CO)4{ 1 ‐κ2P,S}] [M = Mo ( 3 ), W ( 4 )] and [M(CO)4{ 2 ‐κ2P,Se}] [M = Mo ( 5 ), W ( 6 )]. Complexes 3 – 6 were characterized by multinuclear NMR (1H, 13C, 31P, and 77Se NMR) and IR spectroscopy. Crystal‐structure determinations were carried out on 3 , 5 , and 6 , which represent the first examples of structurally characterized complexes of such ligands with group‐6 metal carbonyls. 相似文献
12.
《Journal of organometallic chemistry》1986,301(1):79-90
New anionic carbonylcobalt(I) complexes [X2Co(CO)2(PPh3)](PR4) (X=Cl, PR4 = PBzPh3 (I); X = Br, PR4 = PEtPh3 (II)) have been prepared by reduction of the cobalt(II) halides with NaBH4 in the presence of PPh3 and the phosphonium salt PR4X. Cleavage of halide bridges in dimeric or polymeric [XCo(PPh3)2]n and [XCo(PPh3)]n gives the neutral dicarbonyl derivatives XCo(CO)2PPh3)2. Treatment of ClCo(CO)2(PPh3)2 with alkylating agents gives the known σ- and η- organocobalt(I) derivatives, and reactions with TIClO4 in the presence of various amounts of different mono- and bi-dentate phosphines give the cationic tricarbonyl [Co(CO)3(PPh3)2]+, dicarbonyl [Co(CO)2(PMePh2)3]+ and monocarbonyl [Co(CO)L4]+ complexes (L4 = 4P(OMe)3, 2 dppe and 2dppm). The dppm complex crystallizes in the monoclinic space group P21/c with a 17.895(6), b 10.751(2), c 24.687(4) Å, β 98.92(1)°, and Dcalc 1.35 g cm−3 for Z = 4. A final R value of 0.077 ( Rw = 0.061), based on 2656 observed reflections, was obtained. The cobalt atom exhibits a distorted trigonal bipyramidal geometry. The perchlorate anion is severely disordered or freely rotating. 相似文献
13.
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
14.
The kinetics of the reactions of methoxyorganylcarbenechromium complexes Cr(CO)5C(OCH3)R′ (R′ = CH3, C6H5) with tertiary phosphines PR3 have been studied by means of spectrophotometric methods. The reaction products of general composition cis-Cr(CO)4(PR3)C(OCH3)R′, Cr(CO)5PR3 and trans-Cr(CO)4(PR3)2 are formed by cleavage of both the Cr-CO and the Cr-C(carbene) bonds. The two-term rate law indicates two parallel, dissociative and associative, mechanisms. The kinetic data will be discussed in connection with the concept of labilising and non-labilising ligands. 相似文献
15.
The Simplest Amino‐borane H2B=NH2 Trapped on a Rhodium Dimer: Pre‐Catalysts for Amine–Borane Dehydropolymerization
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Amit Kumar Nicholas A. Beattie Dr. Sebastian D. Pike Prof. Stuart A. Macgregor Prof. Andrew S. Weller 《Angewandte Chemie (International ed. in English)》2016,55(23):6651-6656
The μ‐amino–borane complexes [Rh2(LR)2(μ‐H)(μ‐H2B=NHR′)][BArF4] (LR=R2P(CH2)3PR2; R=Ph, iPr; R′=H, Me) form by addition of H3B?NMeR′H2 to [Rh(LR)(η6‐C6H5F)][BArF4]. DFT calculations demonstrate that the amino–borane interacts with the Rh centers through strong Rh‐H and Rh‐B interactions. Mechanistic investigations show that these dimers can form by a boronium‐mediated route, and are pre‐catalysts for amine‐borane dehydropolymerization, suggesting a possible role for bimetallic motifs in catalysis. 相似文献
16.
Complexes of aromatic or α,β-unsaturated nitriles YCN of the type (YCN)2(PR3)2Mo(CO)2 and (YCN)(PR3)3Mo(CO)2 are new chromophores. Their intense electronic absorption band in the visible spectrum is strongly influenced by substituents and solvent polarity. Acceptor properties of nitriles are discussed on the basis of CNDO-calculations. CT-character and solvato-chromism can be interpreted in terms of the back-bonding ability of the nitriles in electron-rich metal complexes. 相似文献
17.
Karl S Coleman Simon Turberville Sofia I Pascu Malcolm L.H Green 《Journal of organometallic chemistry》2004,689(4):770-774
New ferrocenyl phosphane ligands incorporating Si-P linkages, [(η-C5H4SiMe2PR2)2Fe], where R=Ph and Me, and the corresponding metal complexes [Mo(CO)4(L)] have been prepared and characterised. The molecular structures of [(η-C5H4SiMe2PR2)2Fe], where R=Ph and Me have been determined by single crystal X-ray diffraction. 相似文献
18.
Metal Complexes of Biological Important Ligands. LXXXII. Triphenylphosphine Molybdenum, Tungsten, Ruthenium, and Iridium Complexes of N-Acyl-α-Aminocarboxylates The reactions of the hydrido complexes RuHCl(CO) · (PPh3)3, RuH2(PPh3)4 and IrH3(PPh3)3 with N-acyl-α-aminocarboxylates give the carboxylate complexes RuCl(O2CCHRNHCOR′)(CO)(PPh3)2 ( 1–3 ), RuH(O2CCHRNHCOR′)(PPh3)3 ( 4–6 ) and IrH2(O2CCH2NHCOPh)(PPh3)3 ( 7 ). The structure of RuCl · (O2CCHNHCOPh)(CO)(PPh3)2 ( 1 ) has been determined by x-ray diffraction. The triphenylphosphine complexes MBr · (O2CCH2NHCOR)(CO)2(PPh3)2 (M = Mo, W) ( 8–12 ) and Mo(O2CCHRNHCOR′)2(CO)2(PPh3)2 ( 13–17 ) are formed from MBr2(CO)2(PPh3)2 (M = Mo, W) with one or two equivalents of N-acyl-a-aminoacidates, respectively. 相似文献
19.
F.Albert Cotton Donald J. Darensbourg Brian W.S. Kolthammer 《Journal of organometallic chemistry》1981,217(1):C14-C16
The reactions of M2Cl4(PR3)4 derivatives (M Mo, W and PR3 PEt3, PBu3n) with CO at atmospheric pressure in toluene at 70°C to afford M(CO)3(PR3)2Cl2 and trans-M(CO)4(PR3)2 are reported. 相似文献
20.
Reactions of one or two equiv. of cyclohexyl isocyanide in THF at room temperature with Mo?Mo triply bonded complexes [Mo(CO)2(η5‐C5H4R)]2 (R=COCH3, CO2CH3) gave the isocyanide coordinated Mo? Mo singly bonded complexes with functionally substituted cyclopentadienyl ligands, [Mo(CO)2(η5‐C5H4R)]2(μ‐η2‐CNC6H11) ( 1a , R=COCH3; 1b , R=CO2CH3) and [Mo(CO)2(η5‐C5H4R)(CNC6H11)]2 ( 2a , R=COCH3; 2b , R=CO2CH3), respectively. Complexes 1a , 1b and 2a , 2b could be more conveniently prepared by thermal decarbonylation of Mo? Mo singly bonded complexes [Mo(CO)3(η5‐C5H4R)]2 (R=COCH3, CO2CH3) in toluene at reflux, followed by treatment of the resulting Mo?Mo triply bonded complexes [Mo(CO)2(η5‐C5H4R)]2 (R=COCH3, CO2CH3) in situ with cyclohexyl isocyanide. While 1a , 1b and 2a , 2b were characterized by elemental analysis and spectroscopy, 1b was further characterized by X‐ray crystallography. 相似文献