Novel five-coordinate organoiridium(I) complexes of the type Ir(R)(CO)(chel-P3) (chel-P3=PhP(CH2CH2CH2PPh2)2: R = CH2CMe3, CH2SiMe3; chel-P3 = MeP-(CH2CH2CH2PPh2)2: R = CH2SiMe3; chel-P3PhP(CH2CH2PPh2)2; R = CH2SiMe3, 4-MeC6H4) have been prepared from Ir(R)(CO)(PPh3)2 and the respective triphosphine. According to 31P NMR, these compounds are stereochemically rigid at normal temperatures. The reaction of Rh(R)(CO)(PPh3)2, where R = CH2CMe3 or 2-MeC6H4, with PhP(CH2CH2CH2PPh2)2 yielded the four-coordinate derivatives Rh(CH2CMe3)[PhP(CH2CH2CH2PPh2)2] and Rh(2-MeC6H4)[PhP(CH2CH2CH2PPh2)2]), which arealready known from the literature. 相似文献
The organorhodium(I) complexes Rh(R)[PhP(CH2CH2CH2PPh2)2] (R CH2CMe3, CH2SiMe3; 2-MeC6H4, 4-MeC6H4, 2,4-Me2C6H3, 2,4,6-Me3C6H2; C2Ph) have been prepared and characterized by 31P and 1H NMR spectroscopy and an X-ray structure determination of the tolyl derivative Rh(2-MeC6H4)-[PhP(CH2CH2CH2PPh2)2].For these compounds, the relative 31P coordination shifts Δ(PPh2) > Δ(PPh) distinctly reflect the electron-releasing properties of the organoligands σ-bonded trans to PPh. As expected, coupling between the 103Rh nucleus and phenylphosphino P atoms is weak and varies only little as the strong trans influence groups R are changed. In contrast to this insensitivity of 1J(Rh-PPh) to R, Rh-P coupling within the Ph2P-Rh-PPh2 moieties shows considerable dependence upon the nature of the C-donor producing the cis influence series sp3-C <sp2-C < sp-C.The ortho-tolyl complex crystallizes from toluene as 1/1 solvate Rh(2-MeC6H4)[PhP(CH2CH2CH2PPh2)2] · C7H8. Crystals are orthorhombic, space group Pbc21, with a 1017.9(7), b 1974.3(14), c 2177.6(11) pm, and Z = 4. The structure has been refined to R = 0.079 for 2249 unique data with F0 > 3σ(F0). Metal-phosphorus distances are 225.7(5) and 229.6(6) pm for Rh-PPh2 and 227.3(6) pm for Rh-PPh. 相似文献
Substituted phosphines of the type Ph2PCH(R)PPh2 and their PtII complexes [PtX2{Ph2PCH(R)PPh2}] (R = Me, Ph or SiMe3; X = halide) were prepared. Treatment of [PtCl2(NCBut)2] with Ph2PCH(SiMe3)-PPh2 gave [PtCl2(Ph2PCH2PPh2)], while treatment with Ph2PCH(Ph)PPh2 gave [Pt{Ph2PCH(Ph)PPh2}2]Cl2. Reaction of p-MeC6H4C≡CLi or PhC≡CLi with [PtX2{Ph2PCH(Me)PPh2}] gave [Pt(C≡CC6H4Me-p)2-{Ph2PCH(Me)PPh2}] (X = I) and [Pt{Ph2PC(Me)PPh2}2](X = Cl),while reaction of p-MeC6H4C≡CLi with [Pt{Ph2PCH(Ph)PPh2}2]Cl2 gave [Pt{Ph2PC(Ph)PPh2}2]. The platinum complexes [PtMe2(dpmMe)] or [Pt(CH2)4(dpmMe)] fail to undergo ring-opening on treatment with one equivalent of dpmMe [dpmMe = Ph2PCH(Me)PPh2]. Treatment of [Ir(CO)Cl(PPh3)2] with two equivalents of dpmMe gave [Ir(CO)(dpmMe)2]Cl. The PF6 salt was also prepared. Treatment of [Ir(CO)(dpmMe)2]Cl with [Cu(C≡CPh)2], [AgCl(PPh3)] or [AuCl(PPh3)] failed to give heterobimetallic complexes. Attempts to prepare the dinuclear rhodium complex [Rh2(CO)3(μ-Cl)(dpmMe)2]BPh4 using a procedure similar to that employed for an analogous dpm (dpm = Ph2PCH2PPh2) complex were unsuccessful. Instead, the mononuclear complex [Rh(CO)(dpmMe)2]BPh4 was obtained. The corresponding chloride and PF6 salts were also prepared. Attempts to prepare [Rh(CO)(dpmMe)2]Cl in CHCl3 gave [RhHCl(dpmMe)2]Cl. Recrystallization of [Rh(CO)(dpmMe)2]BPh4 from CHCl3/EtOH gave [RhO2(dpmMe)2]BPh4. Treatment of [Rh(CO)2Cl2]2 with one equivalent of dpmMe per Rh atom gave two compounds, [Rh(CO)(dpmMe)2]Cl and a dinuclear complex that undergoes exchange at room temperature between two formulae: [Rh2(CO)2(μ-Cl)(μ-CO)(dpmMe)2]Cl and [Rh2(CO)2-(μ-Cl)(dpmMe)2]Cl.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
By reaction of [Ir(COD)Cl]2 (COD = 1,5-cyclooctadiene) with i-C3H7MgBr in the presence of cyclic dienes, complexes of the type [IrH(COD)L] (L = 1,3-cyclohexadiene, 2-methyl-],3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene) are obtained. The system IrCl3/i-C3H7MgBr/1,3-C6H8 yields [IrH(1,3-C6H8)2]. According to NMR spectroscopic investigations the pure hydrido forms exist in solution only at low temperatures while at room temperature dynamic H-addition—elimination equilibria of the type [IrH(η4-diene)(COD)] ? [Ir(η3-enyl)(COD)] and [IrH(η4-1,3-C6H8)2] ? [Ir(η3-C6H9)-(η4-1,3-C6H8)], respectively, are observed; the hydrogen at the iridium atom is thereby transferred to the endo positions of the diene ligands. 相似文献
Summary The reaction of previously reported RhI and IrI cationic complexes towards carbon monoxide and triphenylphosphine has been studied. Carbonyl rhodium(I) mixed complexes of the formulae [Rh(CO)L2(PPh3)]ClO4, (L=tetrahydrothiophene(tht), trimethylene sulfide(tms), SMe2, or SEt2), [(CO)(PPh3)Rh{-(L-L)}2Rh(PPh3)(CO)](ClO4)2 (L-L= 2,2,7,7-tetramethyl-3,6-dithiaoctane (tmdto), (MeS)2(CH2)3 (dth), or 1,4-dithiacyclohexane (dt), [Rh(CO)L(PPh3)2]ClO4 (L= tht, tms, SMe2, or SEt2), and carbonyl iridium(I) complexes of the formulae [Ir(CO)2(COD)(PPh3)]ClO4, [Ir(CO)(COD)(PPh3)2]ClO4, [(CO)(COD)(PPh3) Ir{-(L-L)} Ir(PPh3)(COD)(CO)](ClO4)2 (L-L = tmdto or dt), [(CO)2 (PPh3)Ir(-tmdto)Ir(PPh3)(CO)2](ClO4)2, [(CO)2(PPh3) Ir(-dt)2Ir(PPh3)(CO)2](ClO4)2, were prepared by different synthetic methods. 相似文献
Reaction of [RhCl(PPh3)3] with [o-MeC6H4CH2MgBr] affords high yields of the non-fluxional complex, [Rh(CH2C6H4Me)(PPh3)2] which has been shown crystallographically to contain a 1-3-η-benzyl group bound through the phenyl carbon atom that is not substituted with the methyl group. Crystals of this compound are triclinic, space group P, with a = 10.561(6). b = 17.705(3), c = 10.934(4) Å, α = 80.69(3), β = 116.86(4), γ = 102.30(4)° and Z = 2. The structure was solved via the heavy-atom method and refined to R = 0.032 using 5379 diffractometer data with I > 1.56(I). Attempts to prepare π-bonded xylylene complexes from this compound by reaction with base have been unsuccessful, but protonation followed by recrystallisation from acetone gives [Rh{(CH3)2CO}2(PPh3)2]BF4. 相似文献
The reactions of [Rh(CO)2Cl]2 with α-diimines, RN=CR′-CR′=NR (R = c-Hex, C6H5, p-C6H4OH, p-C6H4CH3, p-C6H4OCH3, R′ = H; R = c-Hex, C6H5, p-C6H4OH, p-C6H4OCH3; R′ = Me) in 2:1 Rh/R-dim ratio gave rise to ionic compounds [(CO)2Rh.R-dim(R′,R′)][Rh(CO)2Cl2] which have been characterized by elemental analyses, electrical conductivity, 1H-NMR and electronic and IR spectroscopy. Some of these complexes must involve some kind of metal-metal interaction. The complex [Rh(CO)2Cl.c-Hex-dim(H,H)] has been obtained by reaction of [Rh(CO)2Cl]2 with the c-Hex-dim(H,H) ligand in 1:1 Rh/R-dim ratio. The reactions between [(CO)2Rh.R-dim(H,H)][Rh(CO)2Cl2](R = c-Hex or p-C6H4OCH3) with the dppe ligand have been studied. The known complex RhCl(CO)(PPh3)2 has been isolated from the reaction of [(CO)2Rh.R-dim(H,H)]-[Rh(CO)2Cl2] (R = c-Hex or p-C6H4OCH3) with PPh3 ligand. 相似文献
Summary The rhodium(I) carbonyl compounds [Rh(CO)L22] [BF4]. 1/2CH2Clnn2 (L = PPh2 or AsPh3) react with the nucleophiles OMe−, RCOO− (R = Me, Et) under nitrogen to form [Rh(OR)(CO)L2] (1)–(2) and [Rh(OOCR)(CO)L2] (7)–(10), respectively. Addition of [Rh(CO)2(PPh3)2]-[BF 4] to OMe− under nitrogen produces [Rh(COOMe)-(CO) (PPh3)2]-MeOH (3), whilst reactions of [Rh(CO)-(PPh3)2] [BF4]·1/2CH2Cl2 and [Rh(CO)2(PPh3)2] [BF4] with OR- (R = Me, Et or n-Pr) in the presence of CO produce [Rh(COOR)(CO)2(PPh3)2] (4)–(6). The products have been characterised by i.r., 1H, 31P, 13Cn.m.r. spectroscopy and elemental analysis. 相似文献
[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
Synthesis, Structure, and Photochemical Behavior of Olefine Iridium(I) Complexes with Acetylacetonato Ligands The bis(ethene) complex [Ir(κ2‐acac)(C2H4)2] ( 1 ) reacts with tertiary phosphanes to give the monosubstitution products [Ir(κ2‐acac)(C2H4)(PR3)] ( 2 – 5 ). While 2 (R = iPr) is inert toward PiPr3, the reaction of 2 with diphenylacetylene affords the π‐alkyne complex [Ir(κ2‐acac)(C2Ph2)(PiPr3)] ( 6 ). Treatment of [IrCl(C2H4)4] with C‐functionalized acetylacetonates yields the compounds [Ir(κ2‐acacR1,2)(C2H4)2] ( 8 , 9 ), which react with PiPr3 to give [Ir(κ2‐acacR1,2)(C2H4)(PiPr3)] ( 10 , 11 ) by displacement of one ethene ligand. UV irradiation of 5 (PR3 = iPr2PCH2CO2Me) and 11 (R2 = (CH2)3CO2Me) leads, after addition of PiPr3, to the formation of the hydrido(vinyl)iridium(III) complexes 7 and 12 . The reaction of 2 with the ethene derivatives CH2=CHR (R = CN, OC(O)Me, C(O)Me) affords the compounds [Ir(κ2‐acac)(CH2=CHR)(PiPr3)] ( 13 – 15 ), which on photolysis in the presence of PiPr3 also undergo an intramolecular C–H activation. In contrast, the analogous complexes [Ir(κ2‐acac)(olefin)(PiPr3)] (olefin = (E)‐C2H2(CO2Me)2 16 , (Z)‐C2H2(CO2Me)2 17 ) are photochemically inert. 相似文献
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
The reactions of the organometallic 1,4-diazabutadienes, RN=C(R′)C(Me)=NR″ [R = R″ = p-C6H4OMe, R′ = trans-PdCl(PPh3)2 (DAB); R = p-C6H4OMe, R″ = Me, R′ = trans-PdCl(PPh3)2 (DABI; R = R″ = p-C6H4OMe, R′ = Pd(dmtc)-(PPh3), dmtc = dimethyldithiocarbamate (DABII); R = R″ = p-C6H4OMe, R′ = PdCl(diphos), diphos = 1,2-bis(diphenylphosphino)ethane (DABIII)] with [RhCl(COD)]2 (COD = 1,5-cyclooctadiene, Pd/Rh ratio = ) depend on the nature of the ancillary ligands at the Pd atom in group R′. In the reactions with DAB and DABI transfer of one PPh3 ligand from Pd to Rh occurs yielding [RhCl(COD)(PPh3)] and the new binuclear complexes [Rh(COD) {RN=C(R?)-C(Me)=NR″}], in which the diazabutadiene moiety acts as a chelating bidentate ligand. Exchange of ligands between the two different metallic centers also occurs in the reaction with DABII. In this case, the migration of the bidentate dmtc anion yields [Rh(COD)Pdmtc] and [Rh(COD) {RN=C(R?)C(Me)=NR″}]. In contrast, the reaction with DABIII leads to the ionic product [Rh(COD)- (DABIII)][RhCl2(COD)], with no transfer of ligands. The cationic complex [Rh(COD)(DABIII)]+ can be isolated as the perchlorate salt from the same reaction (Pd/Rh ratio = 1/1) in the presence of an excess of NaClO4. In all the binuclear complexes the coordinated 1,5-cyclooctadiene can be readily displaced by carbon monoxide to give the corresponding dicarbonyl derivatives. The reaction of [RhCl(CO)2]2 with DAB and/or DABI yields trinuclear complexes of the type [RhCl(CO)2]2(DAB), in which the diazabutadiene group acts as a bridging bidentate ligand. Some reactions of the organic diazabutadiene RN=C(Me)C(Me)=NR (R = p-C6H4OMe) are also reported for comparison. 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
The syntheses of the novel complexes ((PPh3)2N)(PhC2AuC2Ph)(MC2R) (I: M = Au, R = Ph; II: M = Ag, R = p-MeC6H4)and ((PPh3)2N)(PhC2AuC2Ph)(AuC2Ph)(CuC2-p-MeC6H4) (III) are described and structures considered. 相似文献
Summary Reactions of cinnamonitrile (trans-PhCH=CHCN) with [M(ClO4)(CO)(PPh3)2] (M=Rh or Ir) produce hydrogenation oftrans-PhCH=CHCN to PhCH2CH2CN at 100°C under 3 atm of hydrogen. 相似文献
ortho-Substituted aryliridium(I) complexes of the type [Ir(RnC6H5-n)(CO)L2] (RnC6H5-n = 2-EtC6H4; 2,6-Et2C6H3; L = PPh3 PMePh2) have been prepared from [IrCl(CO)L2] and the corresponding aryllithiums. With the exception of trans-[Ir(2-EtC6H4)(CO)(PPh3)2] these compounds show cis, trans isomerism. After separation, the isomers have been studied by NMR (1H, 31P), IR, and UV-VIS spectroscopy. ab]Durch Umsetzung von [IrCl(CO)L2] (L = PPh3, PMePh2) mit den entsprechenden Lithiumarylen wurden ortho-substituierte Aryliridium(I)-Komplexe des Typs [Ir(Rn C6H5-n)(CO)L2] (RnC6H5?n = 2-EtC6H4; 2,6-Et2C6H3; 2-Et-6-MeC6H3) dargestellt. Mit Ausnahme von trans-[Ir(2-EtC6H4)(CO)(PPh3)2] zeigen diese Verbindungen die Erscheinung der cis,trans-Isomerie. Die Isomere wurden getrennt und mit Hilfe NMR- (1H, 31P), IR- und UV/VIS-spektroskopischer Methoden untersucht. 相似文献
Reaction of carbon diselenide in 3 to 1 molar ratio, and areneselenols in equimolar ratio, with trans-IrCl(CO)(PPPh3)2 and PtL4, gives oxidative addition products, IrCl(CO)CSe2)(PPh3)2, Pt(CSe2)L2, IrHCl(CO)(SeC6H4Me-p)(PPh3)2, and PtH(SeR)L2, respectively (R = Ph and p-MeC6H4; L = PPh3 and PPh2Me). However, reactions of PtL4 with an excess of areneselenols afford bis(arylselenide) complexes Pt(SeR)2L2. The configurations of these complexes are discussed on the basis of their IR and PMR spectra. The carbon diselenide adducts are suggested to have configurations similar to the corresponding carbon disulfide adducts. The platinum hydrides are found to exist as a mixture of cis and trans isomers in solution, both the isomers being labile with regard to dissociative exchange of the tertiary phosphine ligands. The trans configurations of Pt(SeR)2(PPh2Me)2 are unambiguously shown by the virtually coupled triplet pattern of the PPh2Me signals. 相似文献
Diphenylphosphorylazide N3P(O)(OPh)2 reacts with Pt(PPh3)3, Pt(PPh3)2(C2H4), trans-RhCl(CO)(PPh3)2, Ru(CO)3(PPh3)2, CoCl2(PPh3)2 and CuCl(PPh3)2 to give the azido complexes Pt(PPh3)2(N3)R, Pt(PPh3)2(N3)2R2, the urylene complex RhCl(PPh3)2(RNCONR) and the phosphine imine complexes Ru(CO)3(RPPh3)2, CoCl2(RNPPh3)2, CuCl(RNPPh3)2, respectively, (RP(O)(OPh)2). The oxidative addition of n-C6F13SO2N3 to Pt(PPh3)4 and Pt(PPh3)2(C2H4) affords the complexes Pt(PPh3)2(N3)R and Pt(PPh3)2(N3)2R2, respectively, (RSO2C6F13. The compounds are characterized by elemental analysis and by their IR spectra. 相似文献
Summary The preparations and characterisation of cationic complexes of the type [Rh(CO)(MeCN)(PR3)2]ClO4, [Rh(CO)L(PR3)2]ClO4 (L=py or 2-MeOpy), [Rh(CO)(L-L)(PR3)2]ClO4 (L-L = bipy or phen) and [Rh(CO)(PR3)3]ClO4 with PR3 = P(p-YC6H4)3 (Y=Cl, F, Me or MeO) are described. 相似文献
Summary Rhodium(I), iridium(I), palladium(II) and platinum(II) complexes of the phosphinoamide ligands, Ph2PCH2CONHR (R = H, HDPA; Me, MDPA; Ph, PDPA) were prepared and characterized by using conductivity data, i.r., 1H and 31P(H) n.m.r. spectral data. Reaction of the ligands with MCl(PPh3)3 and MCl(CO)(PPh3)2 (M = Rh, Ir) in CH2Cl2 under reflux lead to the formation of MCl(PPh3)2 [Ph2PCH2C(O)NHR] and MCl(CO)(PPh3)[Ph2PCH2–C(O)HNR] respectively. The reaction of either K2MCl4 or cis-MCl2(PPh3)2 affords complexes of the type cis-MCl2[Ph2PCH2C(O)NHR]2 (M = Pd, Pt). A similar product results even from the reaction of phosphinoamides with cis-platin. Possible structures are proposed for the complexes based on their physicochemical data 相似文献
