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1.
The complexes trans-MCl2(PMe3)4 (M = Ru, Os) react with CO and P(OMe)3 to give the mono- and disubstituted derivatives trans,mer-MCl2(PMe3)3L (L = CO, P(OMe)3) and all-trans-MCl2(PMe3)2[P(OMe)3]2, respectively. On reaction of trans-RuCl2[P(OMe)3]4 with CO and PMe3, the compounds trans,mer-RuCl2[P(OMe)3]3(CO) and trans,cis,cis-RuCl2(PMe3)2[P(OMe)3]2 are synthesized. The reduction of MCl2(PMe3)2[P(OMe)3]2 with Na/Hg in benzene or toluene via {M(PMe3)2[P(OMe)3]2} as an intermediate leads to subsequent intermolecular addition of the arene and to the aryl(hydrido)metal complexes cis,trans,cis-MH(C6H5)(PMe3)2[P(OMe)3]2 (M = Ru, Os) and MH(C6H4CH3)(PMe3)2[P(OMe)3)2 (M = Os). For M = Ru, in the presence of P(OMe)3, the ruthenium(0) compound Ru(PMe3)2(P(OMe)3]3 is formed. The hydrido(phenyl) complexes react with equimolar amounts of Br2 or I2 by elimination of benzene to produce the dihalogenometal compounds cis,trans,cis-MX2(PMe3)2[P(OMe)3]2. The reaction of trans-RuCl2(PMe3)4 with Na/Hg in the presence of PPh3 leads to the ortho-metallated complex fac-RuH(η2-C6H4PPh2)(PMe3)3, which reacts with CH3I, CS2, COS and HCl to give the compounds mer-RuI(η2-C6H4PPh2)(PMe3)3, fac-Ru(SCHS)(η2-C6H4PPh2)(PMe3)3, fac-Ru(S2CO)(CO)(PMe3)3 and RuCl2(PMe3)3, respectively. The paramagnetic 17-electron complexes [MCl2(PMe3)nL4-n]PF6 are obtained on oxidation of MCl2(PMe3)nL4-n with AgPF6. Their UV spectra exhibit a characteristic CT band. [RuCl2(PMe3)4]PF6 and [OsCl2(PMe3)4]PF6 react with CO and P(OMe)3 by reduction to form the corresponding ruthenium(II) and osmium(II) compounds MCl2(PMe3)nL4-n.  相似文献   

2.
The cyclopentadienylcobalt(I) compounds C5H5Co(PMe3)P(OR)3 (R = Me, Et, Pri) and C5H5Co(C2H4)L (L = PMe3, P(OMe)3, CO) are prepared by ligand substitution starting from C5H5Co(PMe3)2 and C5H5Co(C2H4)2. Whereas the reaction of C5H5Co(PMe3)P(OMe)3 with CH2Br2 mainly gives [C5H5CoBr(PMe3)P(OMe)3]Br, the dihalogenocobalt(III) complexes C5H5CoX2(PMe3) (X = Br, I) are obtained from C5H5Co(CO)PMe3 and CH2X2. Treatment of C5H5Co(CO)PMe3 or C5H5Co(C2H4)PMe3 with CH2ClI at low temperatures produces a mixture of C5H5CoCH2Cl(PMe3)I and C5H5CoCl(PMe3)I, which can be separated due to their different solubilities. The same reaction in the presence of ligand L gives the carbenoidcobalt(III) compounds [C5H5CoCH2Cl(PMe3)L]PF6 in nearly quantitative yields. If NEt3 is used as the Lewis base, the ylide complexes [C5H5Co(CH2PMe3)(PMe3)X]PF6 (X = Br, I) are obtained. The PF6 salts of the dications [C5H5Co(CH2PMe3)(PMe3)L]2+ (L = PMe3, P(OMe)3, CNMe) and [C5H5Co(CH2PMe3)(P(OMe)3)2]2+ are prepared either from [C5H5Co(CH2PMe3)(PMe3)X]+ and L, or more directly from C5H5Co(CO)PMe3, CH2X2 and PMe3 or P(OMe)3, respectively. The synthesis of C5H5CoCH2OMe(PMe3)I is also described.  相似文献   

3.
Reaction of C5H4(SiMe3)2 with Mo(CO)6 yielded [(η5-C5H3(SiMe3)2)Mo(CO)3]2, which on addition of iodine gave [(η5-C5H3(SiMe3)2Mo(CO)3I]. Carbonyl displacement by a range of ligands: [L  P(OMe)3, P(OPri)3,P(O-o-tol)3, PMe3, PMe2Ph, PMePh2, PPh3, P(m-tol)3] gave the new complexes [(η5-C5H3(SiMe3)2 MO(CO)2(L)I]. For all the trans isomer was the dominant, if not exclusive, isomer formed in the reaction. An NOE spectral analysis of [(η5-C5H3(SiMe3)2)Mo(CO)2(L)I] L  PMe2Ph, P(OMe)3] revealed that the L group resided on the sterically uncongested side of the cyclopentadienyl ligand and that the ligand did not access the congested side of the molecule. Quantification of this phenomenon [L  P(OMe)3] was achieved by means of the vertex angle of overlap methodology. This methodology revealed a steric preference with the trans isomer (less congestion of CO than I with an SiMe3 group) being the more stable isomer for L  P(OMe)3.  相似文献   

4.
The cations [Ru(1—3:5—6-η-C8H11)(η6 -1,3,5-cyclooctatriene)]+ (2) and [RuH(COD)L3]+ (5) (COD = cycloocta-1,5-diene, L = PMe2Ph, AsMePh2) are convenient precursors to a range of η5 -dienyl complexes of ruthenium(II); evidence for hydrogen transfer processes is presented.  相似文献   

5.
The synthesis and the characterization of cobalt(I) complexes of the type [Co(diene)(phosphine)3]Y (diene = 1,3-butadiene and isoprene; phosphine = PMe3, PMe2Ph, and HPPh2; Y = ClO4, BF4, or BPh4) are reported. The fluxional nature of the five-coordinate cations [Co(diene)(phosphine)3]+ is shown by variable-temperature NMR spectroscopy (1H and 31P). Low-temperature spectra are consistent with a square-pyramidal structure in which the diene occupies two basal coordination sites.  相似文献   

6.
Substitution of PPh3 from the bidentate acetatohydridoruthenium(II) complex RuH(CH3OCO)(PPh3)3 with various ligands, L, leads to unidentate acetatohydrido compounds with replacement of one, two or all PPh3 ligands depending on L (L = t-BuNC, PF2NMe2, P(OCH2)3CMe, P(OMe)3, dppe). On the other hand acetic acid elimination from RuH(CH3OCO)(PPh3)3 occurs with fluorophosphines to yield zerovalent ruthenium complexes RuL′5 (L′ = PF2NMe2, PF2NC4H8), RuL4(PPh3) (L′ = PF3) and RuL3(PPh3)2 (L′ = PF3).  相似文献   

7.
The sandwich complexes bis(η6-naphthalene)molybdenum(0) ( 1 ), bis(η6-1-methylnaphthalene)molybdenum(0) ( 2 ), and bis(η6-1,4-dimethylnaphthalene)molybdenum(0) ( 3 ) are synthesized by cocondensation of Mo-atoms with the naphthalene ligands. Complexes 1–3 are also obtained by reduction of MoCl5 or MoCl4. 2THF with highly activated Mg in the presence of the naphthalene ligands. Mg was activated by sublimation of the metal in a simple rotating solution reactor. Complex 2 exists as a mixture of regio- and stereoisomers. Three regioisomers, 3a–c , are formed in reactions of Mo-atoms with 1,4-dimethylnaphthalene, whereas 3a , the isomer with the Mo-atom coordinated to the unsubstituted rings, is formed selectively via the reductive method. The ligands in 1–3 are highly labile. CO displaces both naphthalene rings in 2 and 3 to give [Mo(CO)6], while PF3, P(OMe)3, and PMe3 displace only one coordinated naphthalene in 1 to yield the [Mo(η6-naphthalene)L3] complexes 4–6 . In toluene, arene exchange is a competitive process in reactions of 1 with PF3. Complexes 5 (L = P(OMe)3) and 6 (L = PMe3) react with HBF4 to give the cationic metal hydride complexes 8 and 9 . The X-ray crystal structures of [Mo(η6-naphthalene) {P(OMe)3}3] ( 5 ) and [Mo(H)(η6-naphthalene) {P(OMe)3}3][BF4] ( 8 ) are reported.  相似文献   

8.
Announcement     
[Ru(2–6-η-bicyclo[5.1.0]octadienyl)(PMe2Ph)3][PF6], formed from the reaction of cyclooctatetraene with [RuH(COD)(PMe2Ph)3][PF6] (COD = cycloocta-1,5-diene), has been characterised spectroscopically from 1J(CH) coupling constants and an X-ray structural analysis; the bicyclic ligand contains an elongated bridging CC bond (1.63 Å).  相似文献   

9.
The PH bond of dialkylphosphites (dimethylphosphite, 5,5-dimethyl-1,3-dioxa-2-phosphorinane and 4,4,5,5-tetramethyl-1,3-dioxa-2-phospholane) oxidatively adds to irClL2(L = PPh3, AsPh3) and IrCl(PMe2Ph)3 generated in situ to give six-coordinate hydrido(dialkylphosphonato)iridium(III) complexes, e.g. IrHClL2[{(MeO)2-PO}2H] and IrHCl(PMe2Ph)3[PO(OMe)2]. Addition of triphenylphosphine to a solution containing [IrCl(C8H14)2]2 and dimethylphosphite in a 1:2 mol ratio gives a five-coordinate hydrido (dimethylphosphonato)iridium(III) complex IrHCl(PPh3)2{PO(OMe)2}, from which six-coordinate pyridine and acetylacetonato complexes IrHCl(PPh3)2(C5H5N){PO(OMe)2} and IrH(PPh3)2(acac){PO(OMe)2} can be obtained. The ligand arrangements in the various complexes are inferred from IR, 1H and 31P NMR data.  相似文献   

10.
Novel complexes [Pt(C5H6O2)L2] (IVa, L = PPh3; IVb, L = PMePh2, IVc, L = PMe2Ph) were prepared by the reactions of [Pt(acac)2] with tertiary phosphines either at elevated temperature (when L = PPh3) or at room temperature (L = PMePh2 and PMe2Ph), whereas AsPh3 yielded [Pt(acac)(γ-acac)AsPh3] (Id) by the reaction with [Pt(acac)2] even under rigorous conditions. Complexes IV were characterized on the basis of their IR and NMR spectra, elemental analyses and chemical reactions, and a structure which possesses a chelate type “acetylacetonato” ligand involving π-oxoallyl bonding is proposed.  相似文献   

11.
The triple ligand transfer reaction between planar-chiral cyclopentadienyl-ruthenium complexes [Cp′Ru(NCMe)3][PF6] (1) (Cp′ = 1-(COOR2)-2-Me-4-R1C5H2; R1 = Me, Ph, t-Bu) and iron complexes CpFe(CO)(L)X (2) (L = PMe3, PMe2Ph, PMePh2, PPh3; X = I, Br) resulted in the formation of metal-centered chiral ruthenium complexes Cp′Ru(CO)(L)X (3) in moderate yields with diastereoselectivities of up to 68% de. The configurations of some major diastereomers were determined to be by X-ray crystallography. The diastereoselectivity of 3 was under kinetic control and not affected by the steric effect of the substituents on the Cp′ ring of 1 and the phosphine of 2. Although the double ligand transfer reaction between [Cp′Ru{P(OMe)3}(NCMe)2][PF6] (7) and CpFe(CO)2X (8) produced Cp′Ru{P(OMe)3}(CO)X (9), the selectivity at the ruthenium center was low.  相似文献   

12.
Reaction of [Pt2Cl2(μ-dppm)2] with ligands, L, in the presence of [PF6- gave stable cationic diplatinum(I) complexes [Pt2L2(μ-dppm)2][PF6]2 where L = PMe2Ph, PMePh2, PPh3, NH3, C5H5N. Reaction of [Pt2(NH3)2(μ-dppm)2][PF6]2 with CO gave [Pt2(CO)2(μ-dppm)2][PF6]2 and an unsymmetrical complex [Pt2(CO)(C5H5N)(μ-dppm)2][PF6]2 was also prepared. The compounds were characterized by vibrational and 1H and 31P NMR spectroscopy and the presence of direct platinumplatinum bonds is indicated.  相似文献   

13.
Direct reduction of WCl6 with PMe3 in toluene at 120°C in a sealed tube affords the complexes [WCl4(PMe3)x] (x = 2, 3). [WCl4(PMe3)3] abstracts oxygen from equimolar amounts of water in wet acetone or tetrahydrofuran to give [WOCl2(PMe3)3] in very high yields. This procedure has been successfully applied to the high yield synthesis of other known oxotungsten(IV) complexes, [WOCl2(PR3)3] (PR3 = PMe2Ph and PMePh2). Metathesis reactions of [WOCl2(PMe3)3] with NaX give [WOX2(PMe3)3] (X = NCO, NCS) and [WOX2(PMe3)] (X = Me2NCS2). The synthesis of the trimethylphosphite analogue, [WOCl2(P(OMe)3)3], is also described and the structures of the new complexes assigned on the basis of IR and 1H and 31P NMR spectroscopy.  相似文献   

14.
Abstract . Treatment of the hydrazine salt [Ru(COD)(H2NNH2)4][BPh4]2 with excess of P(OMe)2Ph in acetone gave a homoleptic complex trans‐[Ru{P(OMe)2Ph}6][BPh4]2, which was characterized by IR, 31P{1H}, 13C{1H}, and 1H NMR spectroscopy, elemental analysis, and X‐ray crystallography. The ruthenium in the complex has distorted octahedral coordination arrangement and bonded to all the six P(OMe)2Ph molecules through the phosphorus atoms.  相似文献   

15.
《Polyhedron》2005,24(3):391-396
The reaction of [(η5-C5Me5)Ru(PPh3)2Cl] (1) with acetonitrile in the presence of excess NH4PF6 leads to the formation of the cationic ruthenium(II) complex [(η5-C5Me5)Ru(PPh3)2(CH3CN)]PF6 (2). The complex (2) reacts with a series of N,N′ donor Schiff base ligands viz. para-substituted N-(pyrid-2-ylmethylene)-phenylamines (ppa) in methanol to yield pentamethylcylopentadienyl ruthenium(II) Schiff base complexes of the formulation [(η5-C5Me5)Ru(PPh3)(C5H4N-2-CHN-C6H4-p-X)]PF6 [3a]PF6–[3f]PF6, where C5Me5 = pentamethylcylopentadienyl, X = H, [3a]PF6, Me, [3b]PF6, OMe, [3c]PF6, NO2, [3d]PF6, Cl, [3e]PF6, COOH, [3f]PF6. The complexes were isolated as their hexafluorophosphate salts. The complexes were fully characterized on the basis of elemental analyses and NMR spectroscopy. The molecular structure of a representative complex, [(η5-C5Me5)Ru(PPh3)(C5H4N-2-CHN-C6H4-p-Cl)]PF6 [3e]PF6, has been established by X-ray crystallography.  相似文献   

16.
Methyl- or phenylN-carboxamido-complexes of platinum(II) Pt(NHCOR')RL2 (L = PEt3, R = Me, R′ = Me, CH = CH2; L = PEt3, R = Ph, R′ = Me; L = PMe2Ph, R = Ph, R′ = Me, Ph; L = PMePh2, R = Ph, R′ =3, R = Ph, R′ = Me) have been prepared by the reaction of KOH with cationic nitrile complexes [PtR(NCR′)L2]BF4. Thermally unstable hydrido-N-carboxamido-complexes could be detected spectroscopically. IR and NMR (1H, 31P) spectra of some of the complexes indicate the existence of a solvent- and temperature-dependent equilibrium between syn-and anti-isomers arising from restricted rotation about the NC bond of the carboxamido-group. The anti-isomer is favoured by nonpolar solvents and by increasing bulk of L. In the complex [PtH(NCCH CH2)(PEt3)2]BF4, IR and NMR spectra show acrlonitrile to be bound through nitrogen, not through the olefinic CC bond.  相似文献   

17.
The complex RuH(η2-CH2PMe2)(PMe3)3 is obtained by reduction of trans-RuCl2(PMe3)4 with Na/Hg in benzene. In contrast to the iron analogue, this complex is configurationally stable on the NMR time scale and does not react with CO or P(OMe)3 under normal conditions, but it does react with the electrophiles MeI, CS2 and NH4PF6 to form RuI(η2-CH2PMe2)(PMe3)3, Ru(η3-S2CHPMe2CH2)(PMe3)3 and [RuH(PMe3)5]PF6, respectively.  相似文献   

18.
Summary The compoundtrans-[MoCl2(PMe2Ph)4] has been prepared by the reduction of MoCl5 (by Mg) or of [MoCl3(PMe2Ph)3] (by LiBun) in the presence of PMe2Ph in tetrahydrofuran (THF). It has eff=2.84 B.M. and crystallises in space group P1 witha=11.591(3),b=12.931(3),c=12.703(3) Å, = 95.28(2), =105.97(2), =103.54(2)°. Refinement of the structure gave R=0.036. The Mo-Cl and Mo-P distances average 2.443(6) and 2.534(8) Å, respectively.Low-valent phosphine complexes of the Group VI metals continue to attract much attention because of their involvement in studies of the catalytic activation of dinitrogen(1), dihydrogen(2, 3), alkenes and alkynes(4). As a by-product during our studies of dinitrogen(1) and hydride(2) complexes of molybdenum and tungsten, we obtainedtrans-[MoCl2- (PMe2Ph)4] as yellow, paramagnetic crystals (eff= 2.84 B.M.). We first obtained the compound during the attempted synthesis ofcis-[Mo(N2)2(PMe2Ph)4] by reduction of MoCl5 with Mg in the presence of PMe2Ph (see Experimental). Upon identification of the compound we found that it could be readily synthesised by treatment of [MoCl3(PMe2Ph)3](5) with LiBun in THF in the presence of PMe2Ph (experimental).The complex was shown to have thetrans structure by x-ray analysis (Figure). Analogues oftrans-[MoCl2(PMe2Ph)4] have been prepared, namely [CrCl2(Me2PCH2CH2PMe2)2](6),trans- [MoCl2(PMe3)4](7), [WCl2(PMe2Ph)4](8) and [WCl2(PMe3)4](4), of which onlytrans-[MoCl2(PMe3)4] has been examined by X-rays(7). Its principal structural parametersi.e. d(Mo-Cl)= 2.420(6), d(Mo-P)av=2.496(3) Å(6) are close to those found here fortrans-[MoCl2(PMe2Ph)4].  相似文献   

19.
A high-yield synthesis of [IrCl(cod)]2 (cod = 1,5-cyclooctadiene) is described. The 1H and 13C NMR spectra of a number of complexes [IrCl(cod)L] are interpreted in terms of a trans-effect series Cl? < sym-collidine < 2-picoline < PCy3 < P-i-Pr3 < Pet3 ~ AsPh3 < PMe2Ph < PMePh2 < PPh2 <P(MeO)Ph2 < PClPh2 < P(OPh)3 < PCl2Ph. Some ligand exchange reactions of [IrCl(cod)L] are discussed. A number of complexes of the type [Ir(cod)Ln]PF6 (L = a variety of amines (n = 2) and phosphines (n = 2 or 3)) are described. Exchange reactions of the sort: [Ir(cod)(PR3)2]PF6 + [Ir(cod)(py)2]PF6 ? [Ir(cod)(PR3)Py]PF6 are reported in which, surprisingly, the isolable mixed ligand complexes are the only detectable species at equilibrium (py = pyridine).  相似文献   

20.
[C5Me5Rh(μ-co)]2 reacts with phosphines (PMe2H, PMe3) and trimethylphosphite to give the binuclear complexes C5Me5(L)Rh(μ-CO)2RhC5Me5 which have been characterised by elemental analyses, mass spectra,1H and 31P NMR data. They are surprisingly inert toward an excess of L and do not react to give the mononuclear compounds C5Me5Rh(CO)L. These are obtained in good yields from C5Me5Rh(CO)2 and L where L is PMe2H, P(OMe)3, PEt3, P(OEt)3 and PMe2Ph.  相似文献   

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