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1.
1,2,3,4,7,7-Hexafluorobicyclo[2.2.1]heptadiene (1) and 2,3-bis(trimethyltin)-1,4,5,6,7,7-hexafluorobicyclo[2.2.1]hepta-2,5-diene (2) react with [M(Ph3P)4] (M = Pt, Pd) to afford air-stable adducts. 2,3-Dichloro-1,4,5,6,7,7-hexafluorobicyclo[2.2.1]hepta-2,5-diene (3) gives only [PtCl2(PPh3)2] with [Pt(Ph3P)4], but a low yield of an adduct was obtained with [Pd(PPh3)4]. The diene 1 also reacts with Fe(CO)5 to form the complex [(C7H2F6)Fe(CO)4], and with [Rh(C2H4)2(acac)] to give [(C7H2F6)Rh(acac)] in which the diene acts as a bidentate ligand. Similar products could not be isolated from the reactions of 2 and 3. A stable adduct, believed to be [{C7F6(SnMe3)2}Rh(CO)2(μ-Cl)2Rh(CO)2] has been isolated from the reaction between 2 and [Rh(CO)2Cl]2. This adduct reacts with PPh3 to give the bridge-cleavage product [{C7F6(SnMe3)2}RhCl(CO)(PPh3)2]. Reaction of 1 with [Rh(CO)2Cl]2 gives an unstable adduct which could not be isolated, and 2 does not react at room temperature. The chloro derivative 3 reacts with [PdCl2(PhCN)2] to give the adduct [(C7F6Cl2)PdCl(PhCN)], but 1 and 2 do not react under similar conditions. Stable substitution products [(C7F6R2)M] (R = H, M = Fe(CO)2(η-C5H5); R = SnMe3, M = Fe(CO)2(η-C5H5), Mn(CO)5, Ir(CO)2(PPh3)2, Rh(CO)2(PPh3)2; R = Cl, M = Ir(CO)2(PPh3)2, Rh(CO)2(PPh3)2) have been isolated from the reactions of the dienes with carbonylmetal anions. Insertion of the CHCH bond occurs when 1 is heated with [MnMe(CO)5] to give [{C7F6H2C(O)Me}Mn(CO)4], and this, on reaction with either PPh3 or [Pt(PPh3)4], gives [(C7F6H2COMe)Mn(CO)4PPh3].  相似文献   

2.
Addition of Cationic Lewis Acids [M′Ln]+ (M′Ln = Fe(CO)2Cp, Fe(CO)(PPh3)Cp, Ru(PPh3)2Cp, Re(CO)5, Pt(PPh3)2, W(CO)3Cp to the Anionic Thiocarbonyl Complexes [HB(pz)3(OC)2M(CS)]− (M = Mo, W; pz = 3,5‐dimethylpyrazol‐1‐yl) Adducts from Organometallic Lewis Acids [Fe(CO)2Cp]+, [Fe(CO)(PPh3)Cp]+, [Ru(PPh3)2Cp]+, [Re(CO)5]+, [ Pt(PPh3)2]+, [W(CO)3Cp]+ and the anionic thiocarbonyl complexes [HB(pz)3(OC)2M(CS)]− (M = Mo, W) have been prepared. Their spectroscopic data indicate that the addition of the cations occurs at the sulphur atom to give end‐to‐end thiocarbonyl bridged complexes [HB(pz)3(OC)2MCSM′Ln].  相似文献   

3.
Metal Complexes of Biologically Important Ligands. CXVII [1] Addition of the O'Donnell Reagent [Ph2C=NCHCO2Me]– to Coordinated, Unsaturated Hydrocarbons of [(C6H7)Fe(CO)3]+, [C7H9Fe(CO)3]+, [(C7H7)M(CO)3]+ (M = Cr, Mo), and [(C2H4)Re(CO)5]+. α-Amino Acids with Organometallic Side Chains The addition of [Ph2C=NCHCO2Me]– to [(C6H7)Fe(CO)3]+, [(C7H9)Fe(CO)3]+, [(C7H7)M(CO)3]+ (M = Cr, Mo) and [(C2H4)Re(CO)5]+ gives derivatives of α-amino acids with organometallic side chains. The structure of [(η4-C6H7)CH(N=CPh2)CO2Me]Fe(CO)3 was determined by X-ray diffraction. From the adduct of [Ph2C=NCHCO2Me]– and [(C7H7)Mo(CO)3]+ the Schiff base of a new unnatural α-amino acid, Ph2C=NCH(C7H7)CO2Me, was obtained.  相似文献   

4.
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   

5.
Summary Carbon monoxide reacts with the cationic dinitrosyls [M(NO)2(PPh3)2]+ (M = Rh, Ir) under ambient conditions to produce CO2, N2O and the tricarbonyl cations, (M(CO)3(PPh3)2]+. The cationic tricarbonyls are reconverted into the dinitrosyl reactants on treatment with NO atca. 80°. The Ru(NO)2(PPh3)2 and Os(NO)2(PPh3)2 complexes react similarly with CO but under more vigorous conditions whereas the corresponding dinitrosyls of cobalt and iron do not undergo this reaction under similar conditions. A pentacoordinate dinitrosyl intermediate [M(NO)2(CO)(PPh3)2]n+ is proposed and a mechanism for the catalytic oxidation of CO by NO is presented. Studies of Pt(N2O2)PPh3)2 establish that a dinitrogcn dioxide intermediate, produced by the coupling of two nitrosyl ligands, is reasonable.  相似文献   

6.
Thiocyanogen and selenocyanogen react with Ru(CO)3(PPh3)2 to give respectively the complexes Ru(CO)2(PPh3)2(NCS)2 and Ru(CO)2(PPh3)2(NCSe)2. (M—NCS and M—SCN represent N- and S-thiocyanato groups, M—NCSe and M—SeCN represent N- and Se-selenocyanato groups respectively, while M—CNS indicates the bridging coordination mode of thiocyanate.) Only the thiocyanogen reacts with Ru3(CO)12 giving [Ru(CO)2(CNS)2]n, which dissolves in hot coordinating solvents, such as pyridine, to form Ru(CO)2(py)2(NCS)2. Selenocyanogen is less effective than thiocyanogen in the oxidative addition reactions with rhodium(I) and iridium(I) complexes; in fact selenocyanogen does not react with Rh(CO)(PPh3)2Cl while with Ir(CO)(PPh3)2Cl the former gives Ir(CO)(PPh3)2(SeCN)2Cl by an equilibrium reaction. The coordination number of the metal and the charge on the complex do not change the bonding mode of the thiocyanate and selenocyanate groups in the iridium(III) complexes; in the Ir(PPh3)2ClX2 and [Ir(Ph2PC2H4PPh2)2X2]+ (X = SCN and SeCN) complexes the pseudohalogens are S- and Se-bonded.The complexes trans-M(PPh3)2(SeCN)2 (M = Pd, Pt) have been obtained by reacting M(PPh3)4 with selenocyanogen.  相似文献   

7.
The reaction of [Pt2(μ-S)2(P-P)2] (P-P=2PPh3, 2PMe2Ph, dppf) [dppf=1,1′-bis(diphenylphosphino)ferrocene] with cis-[M(C6F5)2(PhCN)2] (M=Ni, Pd) or cis-[Pt(C6F5)2(THF)2] (THF=tetrahydrofuran) afforded sulfide aggregates of the type [{Pt2(μ3-S)2(P-P)2}M(C6F5)2] (M=Ni, Pd, Pt). X-ray crystal analysis revealed that [{Pt2(μ3-S)2(dppf)2}Pd(C6F5)2], [{Pt2(μ3-S)2(PPh3)2}Ni(C6F5)2], [{Pt2(μ3-S)2(PPh3)2}Pd(C6F5)2] and [{Pt2(μ3-S)2(PMe2Ph)2}Pt(C6F5)2] have triangular M3S2 core structures capped on both sides by μ3-sulfido ligands. The structural features of these polymetallic complexes are described. Some of them display short metal-metal contacts.  相似文献   

8.
Enhanced reactivity is shown by uncoordinated C≡C bonds in the proximity of a metal in phosphanylacetylene complexes. cis-[Pt(C6F5)2(thf)2] reacts with [M(C6F5)2(PPh2C≡CPh)2] (M=Pt, Pd) to form binuclear complexes containing the novel 2,3-bis(diphenylphosphanyl)-1,3-butadien-1-yl bridging ligand. Substitution of the solvent ligands with, for example, PPh2H (see picture) provides species that could be characterized by X-ray crystallography.  相似文献   

9.
《Polyhedron》1987,6(11):2009-2018
A new bidentate ligand {2-(diphenylphosphino)ethyl}benzylamine(DPEBA) was synthesized and characterized based on the IR, mass and 1H, 13C and 31P NMR spectra. Various complexes of platinum group metal ions and Ni(II) and Co(II) ions with the ligand were synthesized. Reaction of RuCl2(PPh3)3 or RuCl2(Me2SO)4 with the ligand DPEBA, resulted in formation of a penta-coordinate, Ru(II) species of the composition [RuCl(DPEBA)2]Cl. Carbonylation of [RuCl(DPEBA)2]Cl gave an octahedral carbonyl complex of the type [RuCl(CO)(DPEBA)2]Cl. The reaction of RuCl3·3H2O or RuCl3(AsPh3)2MeOH with a twofold excess of the ligand gave an octahedral Ru(III) cationic species [Ru(DPEBA)2Cl2]Cl. Carbonylation of the Ru(III) complex gave rise to a carbonyl complex [RuCl(CO)(DPEBA)2]Cl2. The ligand DPEBA reacts with cobalt(II) chloride in methanol to give the 1 : 1 complex [Co(DPEBA)Cl2]. A series of Rh(I) complexes [Rh(DPEBA)2Cl], [ RhCl(CO)(DPEBA)] and [Rh(DPEBA)2]Cl were synthesized by the reaction of DPEBA with RhCl(PPh3)3, RhCl(CO)(PPh3)2 and [Rh(COD)Cl]2, respectively. Reaction of [Ir(COD)Cl]2 and IrCl(CO)(PPh3)2 with the ligand DPEBA, gave the square-planar complexes [Ir(DPBA)2]Cl and [Ir(DPEBA)(CO)Cl], respectively. Octahedral cationic complexes of the type [M(DPEBA)2Cl2]Cl (M = Rh(III), Ir(III)) were synthesized by the reaction of the ligand DPEBA and rhodium and iridium trichlorides. Reaction of NiCl2·6H2O with DPEBA in 1 : 2 molar equivalents, in boiling butanol gave an octahedral neutral complex [Ni(DPEBA)2Cl2] which readily rearranges to the square-planar complex [Ni(DPEBA)2]Cl2 in methanol. Reaction of Pd(II) and Pt(II) chlorides with DPEBA gave square-planar, cationic complexes of the type [M(DPEBA)2Cl]Cl (M = Pd, Pt). All the complexes were characterized on the basis of their analytical and spectral data.  相似文献   

10.
The complexes[Pt(C2H4)L2] (L = PPh3 or PMePh2) react with 1,4-diphenyl-buta-1,3-diyne to give, successively, mono- and di-platinum compounds [Pt-(PhC4Ph)L2] and [Pt2(PhC4Ph)L4]. Hexa-2,4-diyne and [Pt(C2H4)(PPh3)2] react similarly. In the di-platinum compounds both acetylenic linkages are η2-bonded to platinum atoms, as also occurs in the complex [Pt2{HC2(CH2)2C2H}(PPh3)4] obtained from hexa-1,5-diyne. Reaction of [Pt3(CN-t-Bu)6 with 1,4-diphenylbuta-1,3-diyne and hexa-2,4-diyne affords di-platinum complexes, shown by spectroscopic studies to have structures containing diplatinacyclobutene rings.  相似文献   

11.
Transition Metal Silyl Complexes, 44. — Preparation of the Binuclear Silyl Complexes (CO)3(R3Si)Fe(μ-PR′R′′)Pt(PPh3)2 by Oxidative Addition of (CO)3(R′R′′HP)Fe(H)SiR3 to (C2H4)Pt(PPh3)2 The complexes (CO)3(R′R′′HP)Fe(H)SiR3 ( 1 ) [PHR′R′′ = PHPh2, PH2Ph, PH2Cy; SiR3 = SiPh3, SiPh2Me, SiPhMe2, Si(OMe)3] react with Pt(C2H4)(PPh3)2 to give the dinuclear, silyl-substituted complexes (CO)3(R3Si)Fe(μ-PR′R′′)Pt(PPh3)2 ( 2 ) in high yields. Upon reaction of 2 (R = R′ R′′ = Ph) with CO, the PPh3 ligand at Pt being trans to the PPh2 bridge is exchanged, and (CO)3(Ph3Si)Fe(μ-PPh2)Pt(PPh3)CO ( 3 ) is formed. Complex 3 is characterized by an X-ray structure analysis. The rather short Fe — Si distance [233.9(2) pm] and the infrared spectrum of 3 indicate that the Fe — Pt bond is quite polar.  相似文献   

12.
A detailed study has been made of the halogenation of toluene in the presence of a range of transition metal complexes. Both side-chain and ring chlorination are observed, the favoured route depending on the metal complex. Side-chain halogenation, in the presence of [M(PPh3)4] and MCl2(PPh3)2] (M = Pd, Pt), has been shown to proceed by a free radical chain reaction in which the metal complex acts solely as an initiator. In the presence of, [M2(CO)10] (M = Mn, Re), [Re2(CO)8-(PPh3)2], [Fe2(CO)4(η-cp)2] and [Mo2(CO)6(η-cp)2], ring chlorinated products are formed by a Friedel-Crafts mechanism.  相似文献   

13.
Perfluorocarboxylic acids (RFCOOH) (RF = CF3,C2F5 and (for Rh) C6F5) react with the species [M(NO)2(PPh3)2] (M = Ru, Os) and [M′(NO)(PPh3)3] (M′ = Rh, Ir) to yield new nitrosyl complexes [Ru(OCORF)3(NO)(PPh3)2], [OsH(OCORF)2(NO)(PPh3)2], [Os(OCORF)(NO)2(PPh3)2][OCORF], [Ir(OCORF)(NO)(PPh3)2][OCORF] and [Rh(OCORF)2(NO)(PPh3)2].  相似文献   

14.
Acyl and Alkylidenephosphines. XlX. Molecular and Crystal Structure of 2,4-Bis (dimethyl-amino) ?1,3-diphenyl-l, 3-diphosphetane 4-Methyl-1,2,6-triarsa-tricyclo[2.2.1.02.6]-heptan, CH3C(CH2As)3, ( 1 ) reacts with Ru3(CO)12 to the presumable polymeric [Ru(CO)4CH3C(CH2As)3]n ( 2 ), while no reaction takes place with Os3(CO)12·Os3(CO)11CH3CN forms with 1 at ?20°C Os6(CO)21CH2As)3 ( 3 ). The reaction of 1 and Co2(CO)8 yields [Co2(CO)6CH3C(CH2As)3]n ( 4 ). 1 and Ir(CO)2(p-CH3C6H4NH2)Cl reacts in THF solution to [{Ir(CO)(THF]Cl}3{CH3C(CH2As)3}2] ( 5 ), which contains a μ3-(η2Cη1O) carbonmonoxide. Upon treatment of [(μ-Cl)Ir(C8H12)]2 with 1 [{Ir(C8H12)Cl}9{CH3C(CH2As)3}7] ( 6 ) is obtained. The reaction of 1 with Ir(CO)(PPh3)2Cl yields in THF [Ir(CO)(PPh3)(Cl)CH3C(CH2As)3]2 · THF ( 7a ). Heating of 7a in CH2Cl2 leads to the formation of [Ir(CO)(PPh3)(Cl)CH3C(CH2As)3 · CH2Cl2]2 ( 7b ). Pt(PPh3)3 reacts with 1 in THF to give [Pt(PPh3)CH3C(CH2As)3]2 · THF ( 8 ). The novel compounds are mostly insoluble or slightly soluble. They are characterized by elemental and thermogravimetric analysis, IR and, as far as possible, Raman and NMR Spectra. The results indicate that 1 react with the d8, d9, and d10 systems of the VIIIb metals under oxidative additions.  相似文献   

15.
The elimination of the NCMe ligand in [(C6F5)2Pt(μ-PPh2)2M(NCCH3)2] (M = Pd, Pt) results in the formation of the tetranuclear clusters [Pt2Pd2(μ-PPh2)3(C6F5)3(PPh2C6F5)] 1 and [Pt4(μ-PPh2)4(C6F5)4] 2. The structure of 1 indicates that one of the palladium centres is connected to the rest of the centres through two M-M bonds and two weaker η2-C6H5 and η2-P-C interactions.  相似文献   

16.
Attempts to synthesize complexes of group 6 carbonyl compounds [M(CO)6] (M = Cr, Mo, W) with the carbone C(PPh3)2 ( 1 ) via the photo chemically created adducts [(CO)5M(THF)] lead to quantitative formation of the salts [HC(PPh3)2]2[M2(CO)10] ( 2 , Cr; 3 , Mo; 4 , W). Alternatively, a long-time thermal reaction of [Mo(CO)6] performed with 1 in THF generates a series of products initiated by a Wittig-type reaction. In addition to 3 , minor amounts of [(CO)5MoCCPPh3] ( 8 ), [(CO)5MoO2CC{PPh3}2] ( 5 ), and the carbonate complexes [HC(PPh3)2]2[(CO)5Mo(CO3)Mo(CO)4] ( 6 ) and [HC(PPh3)2]2[(CO)4Mo(CO3)Mo(CO)4] ( 7 ) were found. Compounds 2 , 3 , 5 , 6 , and 7 were characterized by X-ray analyses, 31P NMR, and IR spectroscopy. The water, necessary for the formation of the carbonate, stems from decomposition of THF.  相似文献   

17.
The complex [Ru(SC6F5)2(PPh3)2] has been prepared from [RuCl2(PPh3)3] and [Pb(SC6F5)2] and shown by X-rays to have a pseudo-octahedral structure apparently with two RuHC interactions. It reacts with CO to give [Ru(SC6F5)2-(CO)2(PPh3)2].  相似文献   

18.
Addition of [C7H7][PF6] to iron, ruthenium or osmium alkynyl complexes has given eight cationic cycloheptatrienylvinylidene derivatives [M{C C(C7H7)R}(L)2 (η-C5H5)][PF6] (M = Fe, Ru or Os; R = Me, Pr, Ph or C6F5; L = PPh3, L2 = dppm or dppe; but not all combinations). With Fe(C2Ph)(CO)2(η-C5H5), only [Fe(CO)2(thf)(η-C5H5)][PF6] was obtained. Reactions of the new complexes are characterised by loss of the C7H7 group. The NMR spectra and FAB mass spectra are described in detail.  相似文献   

19.
Phosphonium adduct formation via attack of tri-n-butylphosphine on the cations [(C7H7)M(CO)3]+ (M = Cr, Mo, W) obeys the rate law, Rate = k [complex] [PBu3]. The very similar rate constants for the Cr, Mo and W complexes confirm the similar electrophilicities of the tropylium rings in these cations, and also support the view that there is direct addition to the rings. The related complexes [(C6H7)Fe(CO)3]BF4 and [(C6H6)Mn(CO)3]BF4 also form adducts with PBu3, and the quantitative reactivity order [(C6H7)Fe(CO)3]+ > [(C7H7)Cr(CO)3]+ » [(C6H6)Mn(CO)3]+ (160:60:1) has been established.  相似文献   

20.
Halfsandwich‐Type Complexes of Iridium with Tetramethylcyclopentadienyl as Ligand The iridium(I) complexes [(η5‐C5HMe4)Ir(C2H4)2] ( 2 ) and [(η5‐C5HMe4)Ir(CO)2] ( 4 ), which have been prepared from [IrCl(C2H4)2]2 or [IrCl(CO)3]n and LiC5HMe4, react with tosylchloride as well as with X2 (X = Cl, Br, I) by oxidative addition to yield the corresponding iridium(III) compounds. Treating the complexes [(η5‐C5HMe4)IrX2]n ( 7 — 9 ) with CO or PR3 leads to a cleavage of the halide bridges and to the formation of the mononuclear products [(η5‐C5HMe4)IrX2(CO)] ( 10 , 11 ) and [(η5‐C5HMe4)IrX2(PR3)] ( 12 — 20 ), respectively. The molecular structure of [(η5‐C5HMe4)IrBr2(PiPr3)] ( 18 ) was determined crystallographically. The reactions of 8 (X = Br) and 9 (X = I) with Ph2P(CH2)nPPh2 (n = 1 or 2) afford the bridged compounds [{(η5‐C5HMe4)IrX2}2{μ‐Ph2P(CH2)nPPh2}] ( 21—23 ). The dihalide complexes [(η5‐C5HMe4)IrI2(PPh3)] ( 16 ) and [(η5‐C5HMe4)IrX2(PiPr3)] ( 17—19 ) react with hydride sources to give the dihydrido‐ and monohydrido derivatives [(η5‐C5HMe4)IrH2(PPh3)] ( 24 ) and [(η5‐C5HMe4)IrH(X)(PiPr3)] ( 25—27 ). The related dimethyl and monomethyl compounds [(η5‐C5HMe4)Ir(CH3)2(PiPr3)] ( 28 ) and [(η5‐C5HMe4)IrCH3(I)(PiPr3)] ( 29 ) have been obtained from the dihalide precursors 18 or 19 and CH3MgI in the molar ratio of 1:2 or 1:1, respectively.  相似文献   

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