Reaction between Os[B(OEt)2]Cl(CO)(PPh3)2 and 1,2-ethanediol in the presence of Me3SiCl (1 equivalent) leads to the tethered boryl complex, Cl(CO)(PPh3)2 (1), in which one ethoxy substituent on the boryl ligand is exchanged with one hydroxy group of the 1,2-ethanediol leaving the other OH group available to coordinate to osmium, so giving a six coordinate complex. This formulation is confirmed by crystal structure determination. The same reactants, but with 2 equivalents of Me3SiCl, lead to the yellow, coordinatively unsaturated complex, OsCl(CO)(PPh3)2 (2). Complex (2) adds CO to give OsCl(CO)2 (PPh3)2 (3). Crystal structure determinations of 2 and 3 reveal a very marked difference in the Os-B distances found in the five coordinate complex 2 (2.043(4) Å) and the six coordinate complex 3 (2.179(7) Å). In a reaction similar to that used for forming 2 but with 1,3-propanediol replacing 1,2-ethanediol, the product is OsCl(CO)(PPh3)2 (4). The crystal structure for 4 is also reported. 相似文献
Detailed procedures for the syntheses of Os(CO)2(PPh3)3, Os(CO)(CNR)-(PPh3)3 (R = p-tolyl), Os(CO)(CS)(PPh3)3 and Os(CS)(CNR)(PPh3)3, together with the derived complexes Os(CO)2(CS)(PPh3)2, Os(CO)(CS)(CNR)(PPh3)2, Os(η2-C2H4)(CO)(CNR)(PPh3)2, Os(η2-C2H4)(CO)(CS)(PPh3)2, Os(η2CS2)(CO)2-(PPh3)2, Os(η2CS2)(CO)(CS)(PPh3)2, Os(η2-CS2)(CO)(CNR)(PPh3)2, Os(η2PhC2Ph)(CO)2(PPh3)2 and OsH(C2Ph)(CO)2(PPh3)2 are described. 相似文献
The synthesis and characterization by 1H, 13C, 119Sn NMR and 119Sn Mössbauer spectroscopy of (Z)-1-[2-(triphenylstannyl)vinyl]-1-cycloheptanol,
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(1), and (Z)-1-[2-tri-p-tolylstannyl)vinyl-1-cycloheptanol,
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(2), are described, together with their halodemetallation by I2, Br2 and ICIl to yield derivatives of the types
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(Ar = phenyl or p-tolyl, N = 1, 2; X = I, Br, Cl, respectively). The solid-state structures of four compounds have been determined by X-ray diffraction analysis. In the crystals of
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(1) and
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(2) the Sn atom has a tetrahedral geometry distorted towards trigonal bipyramid as a consequence of a close intramolecular contact with the hydroxyl O(1) atom of 2.742(3) Å and 2.768(3) Å, respectively. A trigonal bipyramidal geometry is found in
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(12) and
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(4), in which significant Sn---O(1) interactions are noted [2.437(8) Å and 2.407(8) Å, respectively]. 相似文献
Reaction between Os(CO)2(PPh3)3 and Me3SnH produces Os(SnMe3)H(CO)2(PPh3)2 (1). Multinuclear NMR studies of solutions of 1 reveal the presence of four geometrical isomers, the major one being that with mutually cis triphenylphosphine ligands and mutually trans CO ligands. Os(SnMe3)H(CO)2(PPh3)2 undergoes a redistribution reaction, at the trimethylstannyl ligand, when treated with Me2SnCl2 giving Os(SnMe2Cl)H(CO)2(PPh3)2 (2). Solutions of 2 again show the presence of four isomers but now the major isomer is that with mutually trans triphenylphosphine ligands and mutually cis CO ligands. The redistribution reaction of 1 with SnI4 produces Os(SnMeI2)H(CO)2(PPh3)2 (3) which exists in solution as only one isomer, that with mutually trans triphenylphosphine ligands and mutually trans CO ligands. Treatment of 3 with I2 cleaves the Os-H bond with retention of geometry giving Os(SnMeI2)I(CO)2(PPh3)2 (4). The crystal structure of 4 has been determined. No isomerization of the trans dicarbonyl complex 4 occurs when 4 is heated, instead there is a formal loss of “MeSnI” and formation of OsI2(CO)2(PPh3)2 (5). 相似文献
o(CO)3 (M = Mo, W; R = Me, Ph, p-MeC6H4) (2) (obtained from (CO)3CpMCH2CCR (1) and Co2(CO)8) to give (CO)3
Cp(CO)2 (3) was further investigated by a crossover experiment. Thus, reaction of an equimolar mixture of 2b (M = W, Cp = η5-C5H5, R = Ph) and 2e (M = W, Cp = η5-C5H4Me; R = p-MeC6H4) with CF3COOH affords only 3b (same M, Cp, and R as 2b) and 3e (same M, Cp, and R as 2e) to show an intramolecular nature of this transformation. Reaction of (CO)3CpWCH2CCPh (1b) with Co4(CO)12 was also examined and found to yield 2b exclusively. Treatment of 1 with Cp2Mo2(CO)4 at 0–5°C provides thermally sensitive compounds, possibly (CO)2Cp
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oCp(CO)2 (5), which decompose at room temperature to give Cp2Mo2(CO)6 as the only isolated product. 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 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
The metallo-phosphaalkenes (η5-C5Me5)(CO)2FeP=C(R)(SiMe3) (Ia: R = SiMe3, Ib: R = Ph) and MeO2C---CC---CO2Me undergo a dipolar [3+2]-cycloaddition to afford the metallo-heterocycles [(η5-C5Me5)(CO)
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=C(R)SiMe3] (IIIa,b) with exocyclic P=C double bonds. 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
FTIR studies of the thermal and photochemical reactions of Os(N(O)H)(CO)Cl2(PPh3)2 (1) are described. Though 1 is relatively stable, it readily reacts when irradiated to form multiple products, including a metal–carbonyl species and N2O, the decomposition product of HNO. The relative yields of products varied depending on whether or not excess CO was present. A model is presented that includes initial photochemical release of HNO from 1 as a significant but not exclusive photoreaction. 相似文献
Reaction between Os(SnClMe2)(κ2-S2CNMe2)(CO)(PPh3)2 and either LiSnMe3 or KSnPh3 produces the distannyl complexes, Os(SnMe2SnMe3)(κ2-S2CNMe2)(CO)(PPh3)2 (1) or Os(SnMe2SnPh3)(κ2-S2CNMe2)(CO)(PPh3)2 (3), respectively. Similarly, reaction between Os(SnClMe2)Cl(CO)2(PPh3)2 (6) and KSnPh3 produces the distannyl complex, Os(SnMe2SnPh3)Cl(CO)2(PPh3)2 (7). In the 119Sn NMR spectra of these stable osmium(II) distannyl complexes both the α-Sn and β-Sn atoms show well-resolved 119Sn-119Sn and 119Sn-117Sn coupling. Each of these three distannyl complexes can be selectively functionalised at the α-Sn atom by reaction with SnCl2Me2 giving Os(SnClMeSnMe3)(κ2-S2CNMe2)(CO)(PPh3)2 (2), Os(SnClMeSnPh3)(κ2-S2CNMe2)(CO)(PPh3)2 (4), and Os(SnClMeSnPh3)Cl(CO)2(PPh3)2 (8), respectively. Treatment of compounds 3 or 7 with iodine also cleaves one α-methyl group, selectively, to give Os(SnIMeSnPh3)(κ2-S2CNMe2)(CO)(PPh3)2 (5), or Os(SnIMeSnPh3)Cl(CO)2(PPh3)2 (9). Crystal structures for complexes 3 and 7 have been determined. 相似文献
In addition to well-known dinuclear phenylselenolato palladium complexes, the reaction of [PdCl2(PPh3)2] and NaSePh affords small amounts of novel trinuclear and hexanuclear complexes [Pd3Se(SePh)3(PPh3)3]Cl (1) and [Pd6Cl2Se4(SePh)2(PPh3)6] (2). Complex 1 is triclinic, P1?, a=13.6310(2), b=16.2596(2), c=16.9899(3) Å, α=83.1738(5), β=78.9882(5), γ=78.7635(5)°. Complex 2 is monoclinic, C2/c, a=25.7165(9), b=17.6426(8), c=27.9151(14) Å, β=110.513(2)°. There are no structural forerunners for 1, but the hexanuclear complex 2 is isostructural with [Pd6Cl2Te4(TeR)2(PPh3)6] (R=Ph, C4H3S) that have been observed as one of the products in the oxidative addition of R2Te2 to [Pd(PPh3)4]. Mononuclear palladium complexes may play a significant role as building blocks in the formation of the polynuclear complexes. 相似文献
A reinvestigation of the reaction of Ir(CO)Cl(PPh3)2, 1 with HSnPh3 has revealed that the oxidative-addition product Ir(CO)Cl(PPh3)2(H)(SnPh3), 2 has the H and SnPh3 ligands in cis-related coordination sites. Compound 2 reacts with a second equivalent of HSnPh3 by a Cl for H ligand exchange to yield the new compound H2Ir(CO)(SnPh3)(PPh3)2, 3. Compound 3 contains two cis- related hydride ligands. Under an atmosphere of CO, 1 reacts with HSnPh3 to replace the Cl ligand with SnPh3 and one of the PPh3 ligands with a CO ligand and also adds a second equivalent of CO to yield the 5-coordinate complex Ir(CO)3(SnPh3)(PPh3), 4. Compound 4 reacts with HSnPh3 by loss of CO and oxidative addition of the Sn-H bond to yield the 6-coordinate complex HIr(CO)2(SnPh3)2(PPh3), 5 that contains two trans-positioned SnPh3 ligands. 相似文献
The silver(I) oxide mediated reactions of the gold(III) dichloride complex [{C6H3(CH2
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uCl2] 2a with thiosalicylic or salicylic acid gives the respective complexes [{C6H3(CH2
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)-2}] 3a (X=S) or 6b (X=O), containing chelating thiosalicylate or salicylate dianion ligands. X-ray studies show that for the thiosalicylate system, the thiosalicylate sulfur atom is trans to the N,N-dimethylamino group, whereas in the structure of the salicylate complex, it is the carboxylate group that is trans to NMe2. Both complexes show puckered metallacycles in the solid state. Electrospray mass spectrometry (ESMS) shows strong [M+H]+ and [2M+H]+ ions for both the gold-thiosalicylate and -salicylate complexes, and these ions possess a high stability towards cone voltage-induced fragmentation. ESMS was also used to identify a minor impurity, the bis(cyclo-aurated) cationic complex [A
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Me2)-2-(OMe)-5}2]+ in the starting dihalide complex 2a and in the product 3a. This complex can be formed by reaction of Me4N[AuCl4] with 2 equivalents of the organomercury precursor [Hg{C6H3(CH2NMe2)-2-(OMe)-5}Cl]. The biological (antitumour, antimicrobial and antiviral) activities are also reported, and these reveal the complexes have moderate to high anti-tumour, antibacterial and antifungal activity. 相似文献
The reactions of [ReX2(η2-N2COPh-N′,O)(PPh3)2] with 4-phenylpyrimidine have been performed. As a result, the two complexes [ReX2(N2COPh)(4-PhPyr)(PPh3)2] (X = Cl, Br) (4-PhPyr = 4-phenylpyrimidine), isostructural in the solid state, have been obtained. The crystal and molecular structures of ([ReCl2(N2COPh)(4-PhPyr)(PPh3)2])2·CHCl3 (1) and ([ReBr2(N2COPh)(4-PhPyr)(PPh3)2])2·CHCl3 (2) have been determined. The electronic structure of [ReCl2(N2COPh)(4-PhPyr)(PPh3)2] has been examined using the density functional theory (DFT) method. The spin-allowed electronic transitions of 1 have been calculated with the time-dependent DFT method, and the UV–Vis spectrum of [ReCl2(N2COPh)(4-PhPyr)(PPh3)2] has been discussed on this basis. 相似文献
1 with osmium tetraoxide proceeded with extremed high diastereoselectivity to give only methyl
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2. Configurations of the new stereogenic centers (C-2,3) in 2 were determined by degradation of the C-5,6,7,8 fragment to the well-known methyl
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7. Transformation of 2 into the required
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10, was achieved by a methodology that implied, protection to 8, reduction of the ester group in 8 to a hydroxymethyl group in 9, and finally deprotection to the free
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10. On the other hand, epoxidation reaction on
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11 afforded only the corresponding 2,3-anhydro derivative 12 with
configuration, as could be demonstrated by degradation to (S)-1,2,4-trimetoxybutane 16, which synthesis is reported herein. 相似文献
The paper presents a combined experimental and computational study of novel rhenium(III) complexes with the picolinate ligand – [ReCl2(pic)(PPh3)2] (1) and [ReBr2(pic)(PPh3)2] (2). Both complexes 1 and 2 have been characterised spectroscopically and structurally (by single-crystal X-ray diffraction). Complex 1 has been additionally studied by magnetic measurement. The magnetic behavior is characteristic of a mononuclear d4 low-spin octahedral Re(III) complex (3T1g ground state) and arises because of the large spin–orbit coupling (ζ = 2500 cm−1), which gives a diamagnetic ground state. DFT and time-dependent (TD)DFT calculations have been carried out for complex 1, and UV–vis spectra of the [ReX2(pic)(PPh3)2] compounds have been discussed on this basis. 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
Reaction between Os(CO)2(PPh3)3 and 3,3-diphenylcyclopropene under quartz-halogen irradiation leads to C(sp2)-H bond activation and the formation of the 3,3-diphenylcyclopropenyl complex, OsH[C3H(Ph-2)2](CO)2(PPh3)2 (1). When complex 1 is heated there is ring-opening of the cyclopropene ring and rearrangement to the 3-phenylindenyl complex, OsH[C9H6(Ph-3)](CO)2(PPh3)2 (2). Compound 1 reacts with HCl forming the 2,2-diphenylcyclopropyl complex, OsCl[C3H3(Ph-2)2](CO)2(PPh3)2 (3). Reaction of either 1 or 3 with excess HCl leads to reversible formation of the hydroxycarbene complex, OsCl2[C(OH)C3H3(Ph-2)2](CO)(PPh3)2 (4), through protonation of the acyl group formed by a migratory insertion reaction involving a carbonyl ligand and the σ-bound 2,2-diphenylcyclopropanyl ligand. An X-ray crystal structure determination of 2 is 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
