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1.
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
2.
Sheng Hua Liu 《Journal of organometallic chemistry》2003,683(2):331-336
Treatment of [Ru(CHCHCH2PPh3)X(CO)(PPh3)2]+ (X=Cl, Br) with KTp (Tp=hydridotris(pyrazolyl)borate) and NaBPh4 produced [TpRu(CHCHCH2PPh3)(CO)(PPh3)]BPh4. Reaction of RuHCl(CO)(PPh3)3 with HCCCH(OEt)2 produced Ru(CHCHCH(OEt)2)Cl(CO)(PPh3)2, which reacted with KTp to give TpRu(CHCHCHO)(CO)(PPh3). Treatment of [TpRu(CHCHCH2PPh3)(CO)(PPh3)]BPh4 with NaN(SiMe3)2 and benzaldehyde produced TpRu(CHCHCHCHPh)(CO)(PPh3). The later complex was also produced when TpRu(CHCHCHO)(CO)(PPh3) was treated with PhCH2PPh3Cl/NaN(SiMe3)2. The bimetallic complex [TpRu(CO)(PPh3)]2(μ-CHCHCHCHC6H4CHCHCHCH) was obtained from the reaction of [TpRu(CHCHCH2PPh3)(CO)(PPh3)]BPh4 with NaN(SiMe3)2 and terephthaldicarboxaldehyde. 相似文献
3.
《Journal of organometallic chemistry》1990,384(3):C61-C64
The unsaturated complexes RuCl(CO)(RC=CHR′)(PPh3)2 react with CO to give the dicarbonyl complexes RuCl(CO)2(RC=CHR′)(PPh3)2 or the η2-acyl complexes RuCl(CO)(O=CC(R)=CHR′)(PPh3)2, depending on the R and R′ groups. The RuCl(CO)(O=CC(Me)=CHMe)(PPh3)2 complex reacts with methanol to give RuCl(CO)(O2CC(Me)=CHMe)(PPh3)2, which structure has been established by an X-ray diffraction study. 相似文献
4.
Dr. José García-Calvo Dr. Jonathan A. Robson Prof. Dr. Tomás Torroba Prof. Dr. James D. E. T. Wilton-Ely 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(62):14214-14222
A series of new ruthenium(II) vinyl complexes has been prepared incorporating perylenemonoimide (PMI) units. This fluorogenic moiety was functionalised with terminal alkyne or pyridyl groups, allowing attachment to the metal either as a vinyl ligand or through the pyridyl nitrogen. The inherent low solubility of the perylene compounds was improved through the design of poly-PEGylated (PEG=polyethylene glycol) units bearing a terminal alkyne or a pyridyl group. By absorbing the compounds on silica, vapours and gases could be detected in the solid state. The reaction of the complexes [Ru(CH=CH-PerIm)Cl(CO)(py-3PEG)(PPh3)2] and [Ru(CH=CH-3PEG)Cl(CO)(py-PerIm)(PPh3)2] with carbon monoxide, isonitrile or cyanide was found to result in modulation of the fluorescence behaviour. The complexes were observed to display solvatochromic effects and the interaction of the complexes with a wide range of other species was also studied. The study suggests that such complexes have potential for the detection of gases or vapours that are toxic to humans. 相似文献
5.
The reactions of [Ru(H)(Cl)(CO)(PPh3)3] with 3,5-di-tert-butyl-o-benzoquinone (dbq) and 3,4,5,6-tetrachloro-o-benzoquinone (tcq) have afforded the corresponding semiquinone complexes [RuII(dbsq)(Cl)(CO)(PPh3)2] and [RuII(tcsq)(Cl)(CO)(PPh3)2], respectively. The reaction of [Ru(H)2(CO)(PPh3)3] with tcq has furnished [RuII(tcsq)(H)(CO)(PPh3)2]. Structure determination of [Ru(dbsq)(Cl)(CO)(PPh3)2] has revealed that it is a model semiquinonoid chelate with two equal C---O lengths ( 1.291(6) and 1.296(6) Å). The complexes are one-electron paramagnetic (1.85μB) and their EPR spectra in fluid media display a triplet structure (g2.00) due to superhyperfine coupling with two trans-31P atoms (Aiso17 G). The stretching frequency of the CO ligand increases by 20 cm−1 in going from [Ru(dbsq)(Cl)(CO)(PPh3)2] to [Ru(tcsq)(Cl)(CO)(PPh3)2] consistent with electron withdrawal by chloro substituents. For the same reason the E1/2 values of the cyclic voltammetric quinone/semiquinone and semiquinone/catechol couples undergo a shift of 500 mV to higher potentials between [Ru(dbsq)(Cl)(CO)(PPh3)2] and [Ru(tcsq)(Cl)(CO)(PPh3)2]. 相似文献
6.
The hydrido-thiocarbonyl osmium(II) complexes OsH2(CS)(PPh3)3, OsHCl(CS)(PPh3)3, OsH(OClO3)(CS)(PPh3)3, OsHCl(CS)(CNR)(PPh3)2 and [OsH(CS)(CO)(PPh3)3]+, (R = p-tolyl), have been derived from OsCl2(CS)(PPh3)3 and [OsH(CS)(CO)(PPh3)3]+, the latter can be deprotonated to give the zerolavent complex, Os(CS)(CO)(PPh3)3. 相似文献
7.
Summary The chlorobenzaldehydes, 2-bromo-4-tolualdehyde and 2-iodobenzaldehyde react with IrCl(CO)(PPh3)2 at 190 to 220° to give PhIrCl2(CO)(PPh3)2,p-tolyl IrBr2(CO)(PPh3)2 and PhIrCl2(CO)(PPh3), respectively. Iodo-and bromobenzene form PhIrCl(Hal)(CO)(PPh3)2 complexes, whereas chlorobenzene does not react under these conditions. Halogen transfer from the aromatic to the metal atom in the reaction of halobenzaldehydes, and halogen extrusion in various homogeneously catalyzed processes, are assumed to follow similar reaction patterns. 相似文献
8.
I. G. Iovel' Yu. Sh. Gol'dberg A. P. Gaukhman M. P. Gavars M. V. Shimanskaya é. Lukevits 《Chemistry of Heterocyclic Compounds》1988,24(10):1138-1145
The hydrosilylation of 2-formylpyridine, 2-formyl-6-methylpyridine, 2-formylfuran, and 2-formyl-5-methylfuran with triethylsilane in the presence of Rh(PPh3)3Cl, Rh(PPh3)3(CO)H, Rh(PPh3)2(C0)Cl, Ru(PPh3)3Cl2, Ru(PPh3)2(CO)2Cl2, and Pd(PPh3)2Cl2 was studied. Silyl ethers of the corresponding hetarylcarbinols were obtained in high yields. The formation of products of dehydrocondensation of the silyl ethers is observed in the hydrosilylation of methyl-substituted aldehydes; this process does not occur in the presence of ruthenium complexes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1372–1380, October, 1988. 相似文献
9.
[OS(η2-CS2Me)(CO)2(PPH3)2]+ and [Ir(η2-CS2Me)Cl(CO)(PPh3)2)+ react with NaBH4 giving OsH(CS2Me)(CO)2(PPh3)2 and IrH(CS2Me)Cl(CO)(PPh3)2 respectively; These compounds contain mutually hydride and η1-dithiomethylester ligands and upon heating undergo 1,2-elimination of MeSH producing Os(CS)(CO)2(PPh3)2 and IrCl(CS)(PPh3)2. 相似文献
10.
Alan Dobson David S. Moore Stephen D. Robinson Michael B. Hursthouse Lucy New 《Polyhedron》1985,4(6):1119-1130
The hydrides [MH(O2CCF3)(CO)(PPh3)2] (M = Ru or Os) react with disubstituted acetylenes PhCCPh and PhCCMe to afford vinylic products [M{C(Ph)CHPh}(O2CCF3)(CO)(PPh3)2] and [M{C(Ph)CHMe}(O2CCF3)(CO) (PPh3)2]/[M{C(Me)CHPh}(O2CCF3)(CO)(PPh3)2] respectively. Acidolysis of these products with trifluoroacetic acid in cold ethanol liberates cis-stilbene and cis-PhHCCHMe respectively thus establishing the cis-stereochemistry of the vinylic ligands. The complexes [M(O2CCF3)2(CO)(PPh3)2] formed during the acidolysis step undergo facile alcoholysis followed by β-elimination of aldehyde to regenerate the parent hydrides [MH(O2CCF3)(CO)(PPh3)2] and thereby complete a catalytic cycle for the transfer hydrogenation of acetylenes. The molecular structure of the methanol-adduct intermediate, [Ru(O2CCF3)2(MeOH)(CO)(PPh3)2] has been determined by X-ray methods and shows that the coordinated methanol is involved in H-bonding with the monodentate trifluoroacetate ligand [MEO-H---OC(O)CF3; O...O = 2.54 Å]. The hydrides [MH(O2CCF3)(CO) (PPh3)2]react with 1,4-diphenylbutadiyne to afford the complexes [M{C(CCPh)CHPh} (O2CCF3)(CO)(PPh3)2]. The ruthenium product, which has also been obtained by treatment of [RuH(O2CCF3)(CO)(PPh3)2] with phenylacetylene, has been shown by X-ray diffraction methods to contain a 1,4-diphenylbut-1-en-3-yn-2-yl ligand. The osmium complexes [Os(O2CCF3)2(CO)(PPh3)2], [OsH(O2CCF3)(CO)(PPh3)2] and [Os{C(CCPh)CHPh}(O2CCF3)(CO)(PPh3)2] all serve as catalysts for the oligomerisation of phenylacetylene. Acetylene reacts with [Ru(O2CCF3)2(CO)(PPh3)2] in ethanol to afford the vinyl complex [Ru(CHCH2)(O2CCF3)(CO)(PPh3)2]. 相似文献
11.
《Journal of organometallic chemistry》1990,395(2):C35-C38
The reactions of K[HB(pz)3] (pz = pyrazol-1-yl) with the coordinatively unsaturated σ-vinyl complexes [Ru(CRCHR)Cl(CO)(PPh3)2] (R = H, Me, C6H5) proceed with loss of a chloride and a phosphine ligand to provide the compounds [Ru(CRCHR)(CO)(PPh3){HB(pz)3}] in high yield. Similar treatment of the complex [Ru(C6H4Me-4)Cl(CO)(PPh3)2] leads to the related σ-aryl derivative [Ru(C6H4Me-4)(CO)(PPh3){HB(pz)3}] whilst the complex [RuClH(CO)(PPh3)3] treated successively with diphenylbutadiyne and K[HB(pz)3] provides the unusual derivative [Ru{C(CCPh)CHPh}(CO)(PPh3){HB(pz)3}]. 相似文献
12.
《Journal of organometallic chemistry》1990,390(2):c57-c60
Reaction of Ru(CO)Cl(CHCHR)(PPh3)2 or Ru(CO)Cl(CHCHR)(PPh3)2L (L = py, Me2Hpz) with 1 equivalent of t-butyl isocyanide gives the alkenyl derivatives Ru(CO)Cl(CHCHR)(PPh3)2(t-BuNC). When an excess of isocyanide is used, further reaction results in intramolecular CO insertion to yield η1-acyl complexes [Ru(COCHCHR) (t-BuNC)3(PPh3)2]Cl. Related complexes were obtained from [Ru(CO)(CHCHR)(MeCN)2(PPh3)2]PF6 and an excess of isocyanide. 相似文献
13.
G.R. Clark C.M. Cochrane W.R. Roper L.J. Wright 《Journal of organometallic chemistry》1980,199(2):C35-C38
The osmium carbyne complex, Os(CR)Cl(CO)(PPh3)2, (R p-tolyl) reacts with Group I halides to form the mixed dimetallocyclopropene species, R)Cl(CO)(PPh3)2, R)Cl(CO)(PPh3)2, R)Cl(CO)(PPh3)2, and [R)Cl(CO)(MeCN)(PPh3)2] ClO4 X-ray crystal structure determination of R)Cl(CO)(PPh3)2 confirms the presence of a three-membered ring and the structure can be viewed as the “acetylene-like” interaction of an osmium—carbon triple bond with AgCl. In acid solution AgCl is precipitated and an alkylidene complex results from proton addition to the carbyne ligand. 相似文献
14.
Re(CO)2(NO)(PPh3)2 reacts with aroyl azides RCON3 (R = C6H5, p-CH3C6H4) in benzene to form isocyanate complexes of formula Re(CO)(NO)-(PPh3)2(RCONCO) (I). When the reaction is carried out in protic solvents such as ethanol, carbamoyl derivatives of formula Re(NCO)(NO)(PPh3)2-(CONHCOR) (II) are obtained, which give Re(NCO)(NO)(PPh3)2(CO)(NHCOR) when dissolved in chloroform, a terminal carbonyl ligand being formed from the carbamoyl group.I can be transformed into II by reaction with gaseous HCl, via [Re(CO)-(NO)(PPh3)2 {C(OH)=NCOR}]+Cl- followed by anion exchange with NaN3. II reacts with mineral acids HX (X = Cl, BF4) to give amide derivatives of formula [Re(NCO)(NO)(PPh3)2(CO)(NH2COR)]+ X- which when X = Cl can be easily transformed into Re(NCO)(NO)(PPh3)2(CO)Cl, the amide ligand being removed. Both the protonation reactions of I and II are reversible. IR and 1H NMR data of the new compounds and the mechanisms of formation of I and II are reported and discussed. 相似文献
15.
Os(η2-CH2O)(CO)2(PPh3)2 reacts with CSe2 to form a metallacycle O]Se)(CO)2(PPh3)2. This compound breaks down to Os(η2-CH2Se)(CO)2(PPh3)2 with probable loss of COSe. An alternative route to Os(η2-CH2Se)(CO)2(PPh3)2 and also Os(η2-CH2Te)(CO)2(PPh3)2 is through reaction of Os(CH2I)I(CO)2(PPh3)2 with SeH? and TeH?, respectively. HCl with Os(η2-CH2E)(CO)2(PPh3)2 (E = Se or Te) gives OsCl(EMe)(CO)2(PPh3)2 while methyl iodide gives [Os(η2-CH2EMe)(CO)2 - (PPh3)2] I. BH4? reacts with these cations to cleave the CE bond and form Os(CH3)(EMe)(CO)2(PPh3)2. 相似文献
16.
Eric W. Ainscough Tom A. James Stephen D. Robinson Jonathan N. Wingfield 《Journal of organometallic chemistry》1973,60(2):C63-C66
Osmium triphenylphosphine complexes, OsH4(PPh3)3, OsH2 (CO)(PPh3)3 and OsHCl(CO)(PPh3)3 react with triphenyl phosphite in boiling organic solvents to yield triphenyl phosphite derivatives which subsequently undergo ortho-metallation reactions. 相似文献
17.
Two pseudohalide hydride carbonyl ruthenium(II) complexes with formulae: [RuH(N3)(CO)(PPh3)3] (1) and [RuH(NCO)(CO)(PPh3)3] (2) have been synthesized by the reactions of [RuHCl(CO)(PPh3)3] with sodium azide or sodium cyanate, respectively, and are compared with the previously described thiocyanate analog [RuH(NCS)(CO)(PPh3)3]. The molecular structures of the new compounds were determined by X-ray crystallography and their spectroscopic properties have been studied. Based on the crystal structures, computational investigations have been carried out in order to determine the electronic structures of the complexes. The electronic spectra were calculated with the use of time-dependent DFT methods, and the electronic spectra of the transitions were correlated with the molecular orbitals of the complexes. 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.
A. B. Antonova O. S. Chudin N. I. Pavlenko W. A. Sokolenko A. I. Rubaylo A. D. Vasiliev V. V. Verpekin O. V. Semeikin 《Russian Chemical Bulletin》2009,58(5):955-963
The reactions of Cp(CO)2Re=C=CHPh (2) with M(PPh3)4 (M = Pd, Pt) gave the μ-vinylidene complexes Cp(CO)2RePd(μ-C=CHPh)(PPh3)2 (3) and Cp(CO)2RePt(μ-C=CHPh)(PPh3)2 (1), respectively. The substitution of Ph2PCH2PPh2 (dppm) for the PPh3 ligands in 1 resulted in the formation of Cp(CO)RePt(μ-C(1)=C(2)HPh)(μ-CO)(dppm) (4). The structure of complex 4 has been determined by single-crystal X-ray diffraction analysis. The structural and spectroscopic characteristics of complexes
1, 3, and 4 were compared with the corresponding parameters of the manganese-containing analogs Cp(CO)2MnPd(μ-C=CHPh)(PPh3)2 (5), Cp(CO)2MnPt(μ-C=CHPh)(PPh3)2 (6) and Cp(CO)2MnPt(μ-C=CHPh)(dppm) (7). 相似文献
20.
《Journal of organometallic chemistry》1990,396(1):C22-C24
The reaction of the hydridometal complex [RuClH(CO)(PPh3)3] with 1,4-diphenyl-butadi-1,3-yne has been investigated and found to proceed with monoinsertion to give a coordinatively unsaturated σ-vinyl complex [Ru-{C(CCPh)CHPh} Cl(CO)(PPh3)2], which is also the major product of the reaction of [RuClH(CO) (PPh3)3] with [Hg(CCPh)2]. 相似文献