Treatment of the bulky iminophosphine ligand [Ph2PCH2C(Ph)N(2,6-Me2C6H3)] (L) with [M(CH3CN)2(ligand)]+n, where for M = Pd(II): ligand = η3-allyl, n = 1, and for M = Rh(I), ligand: 2(C2H4), 2(CO) or cod, n = 0, yields the mono-cationic iminophosphine complexes [Pd(η3-C3H5)(L)][BF4] (1), [Rh(cod)(L)][BF4] (2), [Rh(CO)(CH3CN)(L)][BF4] (3), and cis-[Rh(L)2][BF4] (4). All the new complexes have been characterised by NMR spectroscopy and X-ray diffraction. Complex 1 shows moderate activity in the copolymerisation of CO and ethene but is inactive towards Heck coupling of 4-bromoacetophenone and n-butyl acrylate. 相似文献
The complexes cis-[M(Ph2PC6H4-2-S)2] M=Ni, Pd, Pt were stereoselectively synthesized by transmetallation reactions of [M(Cl)2(NCC6H5)2] M=Pd, Pt or NiCl2·6H2O with [Sn(R)2(Ph2PC6H4-2-S)2] R=Ph, nBu or tBu. The conformation of the Pd and Pt derivatives being unequivocally confirmed by single crystal X-ray diffraction studies showing both metal centers to be into a slightly distorted square planar environment, the main distortion being due to the steric hindrance caused by the aromatic rings in the phosphine moiety. 相似文献
Reaction of Ph2PCC(CH2)5CCPh2 with Os3(CO)10(NCMe)2 affords Os3(CO)10(μ,η2-(Ph2P)2C9H10) (1) and the double cluster [Os3(CO)10]2(μ,η2- (Ph2P)2C9H10)2 (2), through coordination of the phosphine groups. Thermolysis of 1 in toluene generates Os3(CO)7(μ-PPh2)(μ3,η5-Ph2PC9H10) (3) and Os3(CO)8(μ-PPh2)(μ3,η6-Ph2P(C9H10)CO) (4). The molecular structures of 1, 3, and 4 have been determined by an X-ray diffraction study. Both 3 and 4 contain a bridging phosphido group and a carbocycle connected to an osmacyclopentadienyl ring, which are apparently derived from C-P bond activation and C-C bond rearrangement of the dpndy ligand governed by the triosmium clusters. 相似文献
Reactions of Mo(II)-tetraphosphine complex [MoCl2(κ4-P4)] (2; P4 = meso-o-C6H4(PPhCH2CH2PPh2)2) with a series of small molecules have been investigated. Thus, treatment of 2 with alkynes RCCR′ (R = Ph, R′ = H; R = p-tolyl, R′ = H; R = Me, R′ = Ph) in benzene or toluene gave neutral mono(alkyne) complexes [MoCl2(RCCR′)(κ3-P4)] containing tridentate P4 ligand, which were converted to cationic complexes [MoCl(RCCR′)(κ4-P4)]Cl having tetradentate P4 ligand upon dissolution into CDCl3 or CD2Cl2. The latter complexes were available directly from the reactions of 2 with the alkynes in CH2Cl2. On the other hand, treatment of 2 with 1 equiv. of XyNC (Xy = 2,6-Me2C6H3) afforded a seven-coordinate mono(isocyanide) complex [MoCl2(XyNC)(κ4-P4)] (7), which reacted further with XyNC to give a cationic bis(isocyanide) complex [MoCl(XyNC)2(κ4-P4)]Cl (8). From the reaction of 2 with CO, a mono(carbonyl) complex [MoCl2(CO)(κ4-P4)] (9) was obtained as a sole isolable product. Reaction of 9 with XyNC afforded [MoCl(CO)(XyNC)(κ4-P4)]Cl (10a) having a pentagonal-bipyramidal geometry with axial CO and XyNC ligands, whereas that of 7 with CO resulted in the formation of a mixture of 10a and its isomer 10b containing axial CO and Cl ligands. Structures of 7 and 9 as well as [MoCl(XyNC)2(κ4-P4)][PF6](8′) and [MoCl(CO)(XyNC)(κ4-P4)][PF6] (10a′) derived by the anion metathesis from 8 and 10a, respectively, were determined in detail by the X-ray crystallography. 相似文献
[Cp4Fe4(CO)4] (1) reacts with p-BrC6H4Li and MeOH in sequence to afford the functionalized cluster [Cp3Fe4(CO)4(C5H4-p-C6H4Br)] (2), while the reaction of 2 with n-BuLi and MeOH produces [Cp2Fe4(CO)4(C5H4Bu)(C5H4-p-C6H4Br)] (3). The double cluster [Cp3Fe4(CO)4(C5H4)]2(p-C6H4) (4) has been prepared by treatment of [Cp4Fe4(CO)4] with p-C6H4Li2 and MeOH in sequence. The electrochemistry of 2 and 4, as well as the crystal structure of 4 have been investigated. 相似文献
The iridium and rhodium complexes [MCl(CO)2(NH2C6H4Me-4)] (M = Ir or Rh) react with [Os3(μ-H)2(CO)10] to give the tetranuclear clusters [MOs3(μ-H)2(μ-Cl)(CO)12]; the iridium compound being structurally identified by X-ray diffraction. Similarly, [IrCl(CO)2(NH2C6H4Me-4)] and [Rh2(μ-CO)2(η-C5Me5)2] afford the tetranuclear cluster [Ir2Rh2(μ-CO)(μ3-CO)2(CO)4(η-C5Me5)2], also characterised by single-crystal X-ray crystallog 相似文献
The reaction of the labile compound [Re2(CO)8(CH3CN)2] with 2,3-bis(2-pyridyl)pyrazine in dichloromethane solution at reflux temperature afforded the structural dirhenium isomers [Re2(CO)8(C14H10N4)] (1 and 2), and the complex [Re2(CO)8(C14H10N4)Re2(CO)8] (3). In 1, the ligand is σ,σ′-N,N′-coordinated to a Re(CO)3 fragment through pyridine and pyrazine to form a five-membered chelate ring. A seven-membered ring is obtained for isomer 2 by N-coordination of the 2-pyridyl groups while the pyrazine ring remains uncoordinated. For 2, isomers 2a and 2b are found in a dynamic equilibrium ratio [2a]/[2b] = 7 in solution, detected by 1H NMR (−50 °C, CD3COCD3), coalescence being observed above room temperature. The ligand in 3 behaves as an 8e-donor bridge bonding two Re(CO)3 fragments through two (σ,σ′-N,N′) interactions. When the reaction was carried out in refluxing tetrahydrofuran, complex [Re2(CO)6(C14H10N4)2] (4) was obtained in addition to compounds 1-3. The dinuclear rhenium derivative 4 contains two units of the organic ligand σ,σ′-N,N′-coordinated in a chelate form to each rhenium core. The X-ray crystal structures for 1 and 3 are reported. 相似文献
The reaction of [Ru(CO)2(PPh3)3] (1) with o-styryldiphenylphophine (SP) (2) gave [Ru(CO)2(PPh3)(SP)] (3) in 83% yield. This styrylphosphine ruthenium complex 3 can also be synthesized by the reaction of [Ru(p-MeOC6H4NN)(CO)2(PPh3)2]BF4 (4) with NaBH4 and 2 in 50% yield. When “Ru(CO)(PPh3)3” generated by the reaction of [RuH2(CO)(PPh3)3] (8) with trimethylvinylsilane reacted with 2, [Ru(CO)(PPh3)2(SP)] (10) was produced in moderate yield as an air sensitive solid. The spectral and X-ray data of these complexes revealed that the coordination geometries around the ruthenium center of both complexes corresponded to a distorted trigonal bipyramid with the olefin occupying the equatorial position and the C-C bonding in the olefin moiety in 3 and 10 contained a significant contribution from a ruthenacyclopropane limiting structure. Complexes 3 and 10 showed catalytic activity for the hydroamination of phenylacetylene 11 with aniline 12. Ruthenium complex 3 in the co-presence of NH4PF6 or H3PW12O40 proves to be a superior catalyst system for this hydroamination reaction. In the case of the reaction using H3PW12O40 as an additive, ketimines (13) was obtained in 99% yield at a ruthenium-catalyst loading of 0.1 mol%. Some aniline derivatives such as 4-methoxy, 4-trifluoromethyl-, and 4-bromoanilines can also be used in this hydroamination reaction. 相似文献
The 1,5-bis(3,5-dimethyl-1-pyrazolyl)-3-thiapentane ligand (bdtp) reacts with [Rh(COD)(THF)2][BF4] to give [Rh(COD)(bdtp)][BF4] ([1][BF4]), which is fluxional in solution on the NMR time scale. Its further treatment with carbon monoxide leads to a displacement of the 1,5-cyclooctadiene ligand, generating a mixture of two complexes, namely, [Rh(CO)2(bdtp)][BF4] ([2][BF4]) and [Rh(CO)(bdtp-κ3N,N,S)][BF4] ([3][BF4]). In solution, [2][BF4] exists as a mixture of two isomers, [Rh(CO)2(bdtp-κ2N,N)]+ ([2a]+) and [Rh(CO)2(bdtp-κ3N,N,S)]+ ([2b]+; major isomer) rapidly interconverting on the NMR time scale. At room temperature, [2][BF4] easily loses one molecule of carbon monoxide to give [3][BF4]. The latter is prone to react with carbon monoxide to partially regenerate [2][BF4]. The ligands 1,2-bis[3-(3,5-dimethyl-1-pyrazolyl)-2-thiapropyl]benzene (bddf) and 1,8-bis(3,5-dimethyl-1-pyrazolyl)-3,6-dithiaoctane (bddo) are seen to react with two equivalents of [Rh(COD)(THF)2][BF4] to give the dinuclear complexes [Rh2(bddf)(COD)2][BF4]2 ([4][BF4]2) and [Rh2(bddo)(COD)2][BF4]2 ([5][BF4]2), respectively. In such complexes, the ligand acts as a double pincer holding two rhodium atoms through a chelation involving S and N donor atoms. Bubbling carbon monoxide into a solution of [4][BF4]2 results in loss of the COD ligand and carbonylation to give [Rh2(bddf)(CO)4][BF4]2 ([6][BF4]2). The single-crystal X-ray structures of [3][CF3SO3], [5][BF4]2 and [6][BF4]2 are reported. 相似文献
The reactions of [ReOX3(AsPh3)2] and [ReOX3(PPh3)2] with 2-(2′-hydroxyphenyl)-2-benzoxazoline (Hhbo) have been examined and [ReOX2(hbo)(AsPh3)] and [ReOX2(hbo)(PPh3)] (X = Cl, Br) complexes have been obtained. The crystal and molecular structures of [ReOCl2(hbo)(AsPh3)] (1) and [ReOBr2(hbo)(PPh3)] (4) have been determined. The electronic structures of 1 and 4 have been calculated with the density functional theory (DFT) method. The spin-allowed electronic transitions of 1 and 4 have been calculated with the time-dependent DFT method, and the UV–Vis spectra of these complexes have been discussed. 相似文献
The oxidative addition of CH3I to planar rhodium(I) complex [Rh(TFA)(PPh3)2] in acetonitrile (TFA is trifluoroacetylacetonate) leads to the formation of cationic, cis-[Rh(TFA)(PPh3)2(CH3)(CH3CN)][BPh4] (1), or neutral, cis-[Rh(TFA)(PPh3)2(CH3)(I)] (4), rhodium(III) methyl complexes depending on the reaction conditions. 1 reacts readily with NH3 and pyridine to form cationic complexes, cis-[Rh(TFA)(PPh3)2(CH3)(NH3)][BPh4] (2) and cis-[Rh(TFA)(PPh3)2(CH3)(Py)][BPh4] (3), respectively. Acetylacetonate methyl complex of rhodium(III), cis-[Rh(Acac)(PPh3)2(CH3)(I)] (5), was obtained by the action of NaI on cis-[Rh(Acac)(PPh3)2(CH3)(CH3CN)][BPh4] in acetone at −15 °C. Complexes 1-5 were characterized by elemental analysis, 31P{1H}, 1H and 19F NMR. For complexes 2, 3, 4 conductivity data in acetone solutions are reported. The crystal structures of 2 and 3 were determined. NMR parameters of 1-5 and related complexes are discussed from the viewpoint of their isomerism. 相似文献
The complex [Ru(CO)2(triphos-κ2P)Cl2] (1) underwent decarbonylation in dichloromethane solution under air over a period of about two weeks to afford the chelated monocarbonyl complex [Ru(CO)(triphos-κ3P)Cl2] (2). The Single Crystal X-ray structure of 2 showed a slightly distorted metal centred complex. The catalytic activity of one of the complexes [Ru(CO)(triphos-κ3P)Cl2] (2) was examined in the transfer hydrogenation of aromatic carbonyl compounds and was found to be efficient with conversion up to 100% in the presence of isopropanol/NaOH. 相似文献
The synthesis and properties of neutral and cationic complexes of general formulae [{RhCl(diolefin)}2(CH2(pz)2)], [Rh(CO)2 (CH2(pz)2)][RhCl2(CO)2], (Rh(diolefin)(CH2(pz)2)]ClO2, [{Rh(diolefin)(PPh3)}2(CH2(pz)2)](ClO4)2, [Rh(CO)2(CH2(pz)2)]ClO4 and [Rh(CO)(CH2(pz)2)(PPh3)]ClO4 are described. The NMR spectra of [Rh(COD)(CH2(pz)2)]ClO4 complexes are discussed. X-ray structural analysis of [Rh(COD)(CH2(Pz)2)]ClO4 · C2H4Cl2 is presented; the final R factor is 0.061 for 2436 observed data, recorded with Cu-Kα, not corrected for absorption and with the sample inside a capillary. The Rh atom presents a distorted square planar coordination in a mononuclear arrangement. The COD ring has a twisted boat conformation, and the two halves of the CH2(Pz)2 moiety, which are quite similar to one another, form an angle of 47.2(4)°. 相似文献
Two hetero-binuclear complexes [Cp∗CoS2C2(B9H10)][Rh(COD)] (2a) and [Cp∗CoSe2C2(B10H10)][Rh(COD)] (2b) [Cp∗ = η5-pentamethylcyclopentadienyl, COD = cyclo-octa-1,5-diene (C8H12)] were synthesized by the reactions of half-sandwich complexes [Cp∗CoE2C2(B10H10)] [E = S (1a), Se (1b)] with low valent transition metal complexes [Rh(COD)(OEt)]2 and [Rh(COD)(OMe)]2. Although the reaction conditions are the same, the structures of two products for dithiolato carborane and diselenolato carborane are different. The cage of the carborane in 2a was opened; However, the carborane cage in 2b was intact. Complexes 2a and 2b have been fully characterized by 1H, 11B NMR and IR spectroscopy, as well as by elemental analyses. The molecular structures of 2a and 2b have been determined by single-crystal X-ray diffraction analyses and strong metal-metal interactions between cobalt and rhodium atoms (2.6260 Å (2a) and 2.7057 Å (2b)) are existent. 相似文献
Reaction of the iridium tetracarbonylate [PPN][Ir(CO)4] (1a) with triphenylcyclopropenyl tetrafluoroborate [C3Ph3][BF4] afforded two dinuclear species Ir2(CO)4(μ,η1:η2-C3Ph3)(μ,η2:η3-C3Ph3) (2) and Ir2(CO)4(μ,η4:η4-C6Ph6) (3a) resulting from the ring opening and in the latter case, coupling of the resulting acyclic, propenyl ligands. The analogous reaction with [PPN][Rh(CO)4] (1b) afforded only the rhodium analogue for 3a. 相似文献
Cyclodiphosphazanes having donor functionalities such as cis-[tBuNP(OR)]2 (R = C6H4OMe-o (2); R = CH2CH2OMe (3); R = CH2CH2SMe (4); R = CH2CH2NMe2 (5)) were obtained in good yield by reacting cis-[tBuNPCl]2 (1) with corresponding nucleophiles. The reactions of 2-5 with [RuCl2(η6-cymene)]2, [MCl(COD)]2 (M = Rh, Ir), [PdCl2(PEt3)]2 and [MCl2(COD)] (M=Pd, Pt) result in the formation of exclusively monocoordinated mononuclear complexes of the type cis-[{tBuNP(OR)}2MLn-κP] irrespective of the reaction stoichiometry and the reaction conditions. In contrast, 2-5 react with [RhCl(CO)2]2, [PdCl(η3-C3H5)]2, CuX (X=Cl, Br, I) to give homobinuclear complexes. Interestingly, CuX produces both mono and binuclear complexes depending on the stoichiometry of the reactants and the reaction conditions. The mononuclear complexes on treatment with appropriate metal reagents furnish heterometallic complexes. 相似文献
The thiocarbonyl analogue of Vaska’s compound is produced in high yield by first treating IrCl(CO)(PPh3)2 with CS2 and methyl triflate to give [Ir(κ2-C[S]SMe)Cl(CO)(PPh3)2]CF3SO3 (1), secondly, reacting 1 with NaBH4 to give IrHCl(C[S]SMe)(CO)(PPh3)2 (2), and finally heating 2 to induce elimination of both MeSH and CO to produce IrCl(CS)(PPh3)2 (3). When IrCl(CS)(PPh3)2 is treated with Hg(CHCHPh)2 the novel 2-iridathiophene, Ir[SC3H(Ph-3)(CHCHPh-5)]HCl(PPh3)2 (4) is produced. The X-ray crystal structure of the iodo-derivative of 4, Ir[SC3H(Ph-3)(CHCHPh-5)]HI(PPh3)2 (5) confirms the unusual 2-metallathiophene structure. Treatment of IrCl(CS)(PPh3)2 with Hg(CHCPh2)2 produces both a coordinatively unsaturated 1-iridaindene, Ir[C8H5(Ph-3)]Cl(PPh3)2 (6) and a chelated dithiocarboxylate complex, Ir(κ2-S2CCHCPh2)Cl(CHCPh2)(PPh3)2 (7). X-ray crystal structure determinations for 6 and 7 are reported. 相似文献
We have synthesised (Et4N)[ReBr2(NCCH3)2(CO)2] 1 in two steps from [ReBr3(CO)3]2−. Complex 1 is water and air stable and the two Br− ligands are easily exchanged for coordinating solvent molecules such as water. The reactivity of 1 with several ligands such as imidazole (imz) and 2-picolinic acid (2-pic) are easily possible with substitution exclusively occurring in trans-position to the carbonyl groups. The resulting complexes [Re(imz)2(NCCH3)2(CO)2]+ and [Re(2-pic)(NCCH3)2(CO)2] have been isolated and structurally characterised. The two acetonitrile ligands are strongly bound and are not substituted under any conditions. Complex 1 represents therefore the new moiety “trans,cis-[Re(NCCH3)2(CO)2]+” which can be considered as a further building block in organometallic chemistry. 相似文献
The iridium(I) complex [Ir(CO2Me)(CO)2(PPh3)2] undergoes a transesterification reaction with the alcohols CH2C(R)CH2OH (R = H, Me), MeCCCH2CH2OH, and HOCH2CH2OH to afford the complexes [Ir(CO2CH2CH2CMe)(CO)2(PPh3)2] and [Ir(CO2CH2CH2OH)(CO)2(PPh3)2], respectively. In contrast the acetylenic alcohol HCCCH2CH2OH gives [Ir(CCCH2CH2OH)(CO)PPh3)2]. Some reactions of the new complexes are described. 相似文献
Dissymmetric dinuclear complexes (PR3)(CO)(H)2Ir(μ-SBu-t)2Ir(C4F6(CO)-(PR3) (III, R = OMe or Me), which can be described as the juxtaposition of dihydrido and alkyne adducts of Vaska's complex associated through thiolato bridges, were obtained by the reaction of hexafluoro-2-butyne with symmetric dinuclear dihydridoiridium(II) complexes, [Ir(H)(μ-SBu-t)(CO)(PR3)]2(]IrIr) (II). When R = OMe, after the loss of H2, a molecular rearrangement leads to the symmetric dinuclear iridium(II) complex [Ir(μ-SBu-t)(CO)(P(OMe)3)]2(C4F6) (IV). A correlation between the presence of an intense absorption near 230 nm in the UV-visible spectra and the existence of a metal—metal bond is established. A sequence of formation, splitting and re-formation of the metal—metal bond is observed along the series of derivatives obtained from [Ir(μ-SBu-t)(CO)P(OMe)3]2 (I) to IV, via II and III. 相似文献
