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1.
Pentacarbonyl(diethylaminocarbyne)chromium tetrafluoroborate, [(CO) 5− CrCNEt 2]BF 4 (I), reacts with PPh 3 with substitution of CO and formation of trans-tetracarbonyl(diethylaminocarbyne)triphenylphosphanechromium tetra-fluoroborate, trans-[PPh 3(CO) 4CrCNEt 2]BF 4 (III). Substitution of CO by PPh 3 in neutral trans-tetracarbonyl(halo)(diethylaminocarbyne)chromium complexes, trans-X(CO) 4CrCNEt 2 (IVa: X = Br, IVb: X = I), leads in a reversible reaction to the corresponding tricarbonyl complexes, mer-X(PPh 3)(CO) 3− CrNEt 2 (V), PPh 3 occupying the cis-position to the carbyne ligand. With PPh 3 in large excess both reactions follow a first-order rate law. This as well as the activation parameters (Δ H≠ = 104–113 kJ mol −1, Δ S≠ = 64–71 J mol −1 K −1) indicate a dissociative mechanism. 相似文献
2.
The preparation and properties as well as some reactions of a series of arylcarbonylbis(triphenylphosphine)iridium(I) complexes [Ir(Ar)(CO)(PPh 3) 2] (Ar = C 6H 5, C 6F 5, 2-C 6H 4CH 3, 3-C 6H 4CH 3, 4-C 6H 4CH 3, 2-C 6H 4OCH 3, 2,6-C 6H 3-(OCH 3) 2, 4-C 6H 4N(CH 3) 2, 3-C 6H 4Cl, 4-C 6H 4Cl, 4-C 6H 4Cl, 3-C 6H 4CF 3, 4-C 6H 4CF 3) are described, and the most important IR data as well as the 31P NMR parameters of these, without exception trans-planar, compounds are given. Some of the complexes react with molecular oxygen to form well defined dioxygen adducts [Ir(Ar)(O2)(CO)(PPh3)2] (Ar = C6H5, 3-C6H4CH3, 4-C6H4CH3). Complexes with ortho-substituted aryl ligands are not oxygenated. This effect is referred to as a steric shielding of the metal center by the corresponding ortho-substituents. With SO2 the similar irreversible addition compound [Ir(4-C6H4CH3)-(SO2)(CO)(PPh3)2] is obtained. Sulfur dioxide insertion into the Ir---C bond cannot be observed. The first step of the reaction between [Ir(4-C6H4CH3)(CO)(PPh3)2] and hydrogen chloride involves an oxidative addition of HCl to give [Ir(H)(Cl)(4-C6-H4CH3)(CO)(PPh3)2]. Ir---C bond cleavage by reductive elimination of toluene from the primary adduct does not occur except at elevated temperature. 相似文献
3.
The ruthenium(II) complex [RuI 2(Me 2SO) 4] was synthesized and characterized. The Me 2SO ligands are all S-bonded. Reactions of RuI 2(Me 2SO) 4 with ligands containing P, N and S donor atoms have been carried out and the complexes obtained were characterized using different physical methods. [RuI 2L 4] (L= CH 3CN, Me 2SO and py), [RuI 2(CH 3CN) 2(PPh 3) 2] and [RuI 2(CS)(PPh 3) 3] have been synthesized using RuI 3 as the source material and characterized as above. 相似文献
4.
Treatment of ruthenium complexes [CpRu(AN) 3][PF 6] (1a) (AN=acetonitrile) with iron complexes CpFe(CO) 2X (2a–2c) (X=Cl, Br, I) and CpFe(CO)L′X (6a–6g) (L′=PMe 3, PMe 2Ph, PMePh 2, PPh 3, P(OPh) 3; X=Cl, Br, I) in refluxing CH 2Cl 2 for 3 h results in a triple ligand transfer reaction from iron to ruthenium to give stable ruthenium complexes CpRu(CO) 2X (3a–3c) (X=Cl, Br, I) and CpRu(CO)L′X (7a–7g) (L′=PMe 3, PMe 2Ph, PMePh 2, PPh 3, P(OPh) 3; X=Br, I), respectively. Similar reaction of [CpRu(L)(AN) 2][PF 6] (1b: L=CO, 1c: P(OMe) 3) causes double ligand transfer to yield complexes 3a–3c and 7a–7h. Halide on iron, CO on iron or ruthenium, and two acetonitrile ligands on ruthenium are essential for the present ligand transfer reaction. The dinuclear ruthenium complex 11a [CpRu(CO)(μ-I)] 2 was isolated from the reaction of 1a with 6a at 0°C. Complex 11a slowly decomposes in CH 2Cl 2 at room temperature to give 3a, and transforms into 7a by the reaction with PMe 3. 相似文献
5.
The reaction of K[ReH 6(PPh 3) 2] with [RhCl(CO)L 2] [L= PPh 3, 1,2,5-triphenylphosphole (TPP), or P(OMe) 3] leads to the new electronically unsaturated heterobimetallic polyhydride complexes [(CO)(PPh 3) 2HRe(μ-H) 3RhL 2] in moderate-to-good yields. The structures of these complexes have been established on the basis of spectroscopic data, especially 1H and 31P NMR. The bridging hydride ligands are fluxional but there is either a slow or nonexistent exchange between terminal and bridging hydrides. For L = PPh 3 or TPP, protonation with tetrafluoroboric acid affords quantitatively the cationic complexes [(CO)(PPh 3) 2HRe(μ-H) 3RhHL 2] +, isolated as the BF 4− or the BPh 4− salts. 相似文献
6.
Three families of heterobimetallic compounds were obtained by reaction of [Mo(CO) 3(CH 3CN) 2(Cl)(SnRCl 2)] (R = Ph, Me) with P(4-XC 6H 4) 3 (X = Cl, F, H, Me, MeO). The type of compound obtained dependent on the solvent and concentration of the starting compound. So, [Mo(CO) 2(CH 3COCH 3) 2(PPh 3)(Cl)(SnRCl 2)]· nCH 3COCH 3 (R = Ph, n = 0.5; R = Me, n = 1) (type I) and [Mo(CO) 3{P(4-XC 6H 4) 3}(μ-Cl)(SnRCl 2)] 2 (R = Ph, X = Cl, F, H, Me, MeO; R = Me, X = Cl, F) (type II) were isolated from acetone solution in ca 0.05 M and 0.1 M concentrations, respectively. However, [Mo(CO) 3(CH 3CN) {P(4-XC 6H 4) 3}(Cl)(SnRCl 2)] (R = Ph, X = H; R = Me, X = Cl, F, H) (type III) were obtained from dichloromethane solution independently of the concentration used. All new complexes showed a seven-coordinate environment at molybdenum, containing Mo---Cl and Mo---Sn bonds. Mössbauer spectra indicated a four-coordination at tin for type III complexes. 相似文献
7.
Addition of 1,4-dithiols to dichloromethane solutions of [PtCl 2(P-P)] (P-P = (PPh 3) 2, Ph 2P(CH 2) 3PPh 2, Phd 2P(CH 2) 4PPh 2; 1,4-dithiols = HS(CH 2) 4SH, (−)DIOSH 2 (2,3- O-isopropylidene-1,4-dithiol-l-threitol), BINASH 2 (1,1′-dinaphthalene-2,2′-dithiol)) in the presence of NEt 3 yielded the mononuclear complexes [Pt(1,4-dithiolato)(P-P)]. Related palladium(II) complexes [Pd(dithiolato)(P-P)] (P-P=Ph 2P(CH 2) 3PPh 2, Ph 2P(CH 2) 4PPh 2; dithiolato = −S(CH 2) 4S −, (−)-DIOS) were prepared by the same method. The structure of [Pt((−)DIOS)(PPh 3) 2] and [Pd(S(CH 2) 4S)(Ph 2P(CH 2) 3PPh 2)] complexes was determined by X-ray diffraction methods. Pt—dithiolato—SnC1 2 systems are active in the hydroformylation of styrene. At 100 atm and 125°C [Pt(dithiolate)(P-P)]/SnCl 2 (Pt:Sn = 20) systems provided aldehyde conversion up to 80%. 相似文献
8.
The preparations and spectroscopic characteristics are reported of a series of (trimethylgermyl)methyl- and (trimethylstannyl)methylplatinum(II) complexes with diene and P-donor ancillary ligands, cis-Pt(CH 2GeMe 3) 2L 2 (L = PPh 3 or PPh 2Me; L 2 = dppe or cod) and cis-Pt(CH 2SnMe 3) 2L 2 (L = PPh 3; L 2 =cod). Thermolysis of toluene solutions of cis-Pt(CH 2GeMe 3) 2(PPh 3) 2 leads to cis-Pt(Me)(CH 2GeMe 2CH 2GeMe 3)(PPh 3) 2 via β-alkyl migration, after (non-rate-limiting) phosphine dissociation. Estimated activation parameters (Δ H298 K‡ = 126 ± 3 kJ mol −1, Δ S‡ = + 17 ± 7 J mol −1 K −1 and hence Δ 298 K‡ = 121 ± 5 kJ mol −1) suggest that this system is more migration labile than its silicon analogue, primarily as a result of a lower activation enthalpy. While cis-Pt(CH 2GeMe 3) 2(PPh 2Me) 2 reacts similarly but less readily, Pt(CH 2GeMe 3) 2(dppe) 2 is inert at operable temperatures. Thermolysis of Pt(CH 2GeMe 3) 2(cod) generates 1,1,3,3,-tetramethyldi-1,3-germacyclobutane as the major organogermanium product, while from cis-Pt(CH 2SnMe 3) 2(PPh 3) 2, 1,1,3,3-tetramethyldi-1,3-stannacyclobutane predominates. Mechanistic implications are discussed. 相似文献
9.
The binuclear molybdenum(II) complexes [Mo 2(O 2CCF 3) 4(PR 3) 2] (R = Ph, Et) act as templates for the self-condensation of 2-aminobenzaldehyde to give a new class of complexes in which a hydride ion bridges two molybdenum(III) centres, each of which carries a tetradentate macrocyclic ligand (C). The new hydrido complexes [Mo 2(C) 2 (H)(O 2CCF 3) 3(PPh 3) 2] (I), [Mo 2(C) 2(H) 2(O 2CCF 3) 2(PPh 3) 2] (II), and [Mo 2(C) 2 (H) 2(O 2CCF 3) 2(PEt 3) 2] 2 (V) exist in two or more isomeric forms as shown by their IR, 1H, 31P and 19F NMR spectra. Substitution with thiocyanate, nitrate and tetraphenylborate anions gives the new products [Mo 2(C) 2(H)(CO)(NCS) 3(PPh 3) 2] (III), [Mo 2(C) 2 (H) 2(O 2CCF 3)(NO 3)(PPh 3) 2] (IV), [Mo 2(C) 2(H)(O 2CCF 3)(PPh 3) 2](BPh 4) 2 (VI) and [Mo 2(C) 2(H) 2(O 2CCF 3)(PEt 3) 2](BPh 4) (VII), which also exist in isomeric forms. 相似文献
10.
Carbon---hydrogen bond cleavage at the terminal 6-position occurs when hex-5-en-2-one (CH 2=CHCH 2CH 2COMe) oxidatively adds to [Os 3(CO) 10(MeCN) 2] to give [Os 3H(μ-CH=CHCH 2CH 2COMe)(CO) 10], which is completely analogous to the simple vinyl complex [Os 3H(μ-CH=CH 2)(CO) 10]. A minor product from the reaction is [Os 3(CH 3CH=CHCH 2COMe)(CO) 10], an isomer in which double-bond migration has occurred to give the βγ-unsaturated ketone; stabilisation occurs through chelation and ketone coordination. [Os 3H 2(CO) 10] reacts with CH 2=CHCH 2CH 2COMe in refluxing cyclohexane to give a third isomer, [Os 3H(CH 3CH 2C=CHCOMe)(CO) 10], in which further double bond migration has occurred to give the β-unsaturated ketone. Metallation at the β-site gives an Os---C bond as part of a 5-membered chelate ring. Thermolysis of each of the three isomeric decarbonyl species in refluxing cyclohexane or heptane leads to the elimination of an Os(CO) 4 group to give the dinuclear compound [Os 2H(EtC=CHCOMe)(CO) 6] in varying yield. Pathways from γδ to the βγ and finally the β unsaturated ketones may be mapped out. 相似文献
11.
Hydrated rhodium(III) chloride reacts with azobenzene (HAzb) affording RhCl 3(PhNH 2) 2 and the dimeric [(Azb) 2RhCl] 2. The latter reacts with donor ligands to give (Azb) 2RhCl(L), (L=PPh 3, tetrahydrofuran). With [Rh(CO) 2Cl] 2, azobenzene affords an unusual Rh I---Rh III complex, [(Azb) 2RhCl 2Rh(CO) 2], which can also be obtained from [Rh(CO) 2Cl] 2 and [(Azb) 2RhCl] 2. These complexes contain the ortho-metallated (phenylazo)phenyl-2 C,N′ ligand, and their spectroscopic properties are summarised. 相似文献
12.
The reaction of K[H 6ReL 2] with [RuHCl(CO)(PPh 3) 3−x {P(OPr i} 3) x](L 2 = (PMePh 2) 2, dppe, (AsPh 3) 2, or (PPh 3) 2; x = 0, 1 or 2) leads to [L 2(CO)HRe(μ-H) 3RuH(PPh 3) 2−y{P(OPr i) 3} y] ( x = 0 or 1, Y = 0; X = 2, Y = 1(L 2 = PPh 3)) in a first step. Under the reaction conditions most of these complexes react rapidly with the liberated phosphine giving [L 2(CO)Re(μ-H) 3Ru(PPh 3) 3−y- {P(OPr i) 3} y] (L 2 = (PMePh 2) 2 or dppe, Y = 0; L 2 = (PPh 3) 2, Y = 1) as the only iso complexes. The structure of [(PMePh 2) 2(CO)Re(μ-H) 3Ru(PPh 3) 3] has been establishedby X-ray structure analysis. The complex [(PPh 3) 2(CO)Re(μ-H) 3Ru(PPh 3) 2(P(OPr i) 3)] reacts with molecular hydrogen under pressure to generate [L 2(CO)HRe(μ-H) 3RuH(PPh 3)(P(OPr i) 3) as the sole product. 相似文献
13.
The compound [Ru 2(μ-O 2CCH 3) 4(THF) 2]BF 4 (I) containing the Ru 25+ unit was prepared by reaction of Ru 2Cl(μ-O 2CCH 3) 4 with AgBF 4 in THF. This compound, in contrast with Ru 2Cl(μ-O 2CCH 3) 4, is soluble in several polar organic solvents and reacts in THF with OPPh 3 and PPh 3 giving [Ru 2(μ-O 2CCH 3) 4(OPPh 3) 2]BF 4·CH 2Cl 2 (II) and [Ru(μ-O 2CCH 3)(O 2CCH 3)(PPh 3)] n (III), respectively. The complex II has been also obtained as hexafluorophosphate [Ru 2(μ-O 2CCH 3) 4(OPPh 32]PF 6·CH 2Cl 2 (IV) by treatment of Ru 2Cl(μ-O 2CCH 3) 4 with an excess of NOPF 6 and PPh 3 in methanol. In this reaction the triphenylphosphine oxide is generated by oxidation of the triphenylphosphine. 相似文献
14.
Isomerization of phenyl-substituted propargylplatinum(II) complex, trans-Pt(CH 2CCPh)(Cl)(PPh 3) 2 (1) to allenyl complex, trans-Pt(CPh=C=CH 2)(Cl)(PPh 3) 2 (2) was found to be catalyzed by zerovalent complex Pd(PPh 3) 4. The reaction was proposed to proceed through the transfer of the propargyl/allenyl ligand both from Pt(II) to Pd(0) and Pd(II) to Pt(0). The former transfer, which seemingly has a thermodynamic disadvantage, has unambiguously been confirmed to take place; treatment of 1 with Pd(PPh 3) 4 or a mixture of Pd 2(dba) 3 and PPh 3 resulted in the formation of Pd(I) complex, Pd 2(μ-PhCCCH 2)(μ-Cl)(PPh 3) 2 which lies in equilibrium with a mixture of propargyl/allenylpalladium(II) and Pd(0) complexes. 相似文献
15.
Rhodium(II) complexes with dioximes [Rh(Hdmg) 2(PPh 3)] 2 [I] (Hdmg=monoanion of dimethylglyoxime) and [Rh(Hdmg)(ClZndmg)(PPh 3)] 2 [II] catalyse hydroformylation and hydrogenation reactions of 1-hexene at 1 MPa CO/H 2 and 0.5 MPa H 2 at 353 K, respectively. Hydroformylation with complex [I] produces 94% of aldehydes ( n/ iso=2.2) and 6% 2-hexene whereas the second catalyst [II] gives ca. 40% of aldehydes ( n/ iso=2.1) and 60% of 2-hexene. Corresponding Rh(III) complexes are inactive in hydroformylation except of RhH(Hdmg) 2(PPh 3) [III], which shows activity similar to [I]. Complexes [Rh(Hdmg) 2(PPh 3)] 2 [I], [Rh(Hdmg)(ClZndmg)(PPh 3)] 2 [II], RhH(Hdmg) 2(PPh 3) [III] and [Rh(Hdmg) 2(PPh 3) 2]ClO 4 [V] catalyse 1-hexene hydrogenation with an average TON ca. 18 cycles/mol [Rh]×min. Complex [II] has also been found to catalyse hydrogenation of cyclohexene, 1,3-cyclohexadiene and styrene. 相似文献
16.
The title compounds react with unidentate ligands, L, containing either phosphorus or arsenic donor atoms to yield the corresponding compounds of the type Ru(η 5---C 5Me 4Et)(CO)LX; with didentate phosphorus donor ligands the major species formed is the bridged complex {Ru(η 5---C 5Me 4Et)(CO)X} 2{Ph 2P(CH 2) nPPh 2} n = 1, X = Br; n = 2, X = Cl). In contrast, unidentate ligands containing nitrogen donor atoms such as pyridine did not react with Ru(η 5---C 5Me 4Et)(CO) 2Cl although reaction with 1,10-phenanthroline or diethylenetriamine yielded the ionic products [Ru(η 5---C 5Me 4Et)(CO)L] +Cl − (L = phen or (NH 2CH 2CH 2) 2NH). Reaction of Ru(η 5---C 5Me 4Et)(CO) 2Br with AgOAc yielded the corresponding acetato complex Ru(η 5---C 5Me 4Et)(CO) 20Ac. Ru(η 5--- C 5Me 4Et)(CO) 2X reacts with AgY (Y = BF 4 or PF 6) in either acetone or dichloromethane to give the useful solvent intermediates [Ru(η 5---C 5Me 4Et)(CO) 2(solvent)] +Y −, which readily react with ligands L to yield ionic derivatives of the type [Ru(η 5---C 5Me 4Et)(CO) 2L] +Y − (where L = CO, NCMe, py, C 2H 4 or MeO 2CCCCO 2Me). 相似文献
17.
Treatment of the dimer complex [C 5Me 5 (CO) 2 Ru] 2 (1) with HBF 4 in CH 2Cl 2 at room temperature yields the hydrido-bridged dinuclear complex [(C 5Me 5) 2Ru 2(CO) 4H]BF 4 (2), and after refluxing in propionic anhydride [C 5Me 5(CO) 3Ru]BF 4 (5) is obtained, UV-irradiation of 1 in the presence of H 2CHal 2 (Hal = Cl, I) or trimethylphosphine leads to the formation of C 5Me 5(CO) 2Ru-Hal (3a, 3b) or C 5Me 5(CO)(Me 3P)RuH (4) respectively. Exchange reactions of 3a, 3b with LiAlH 4, NaOMe and Me 3 P give the complexes C 5Me 5(CO) 2RuX (6a,6b) (X=H, OMe), C 5Me 5(CO)(Me 3P)Ru-Hal (7a,7b) (Hal = Cl, I) and C 5Me 5(Me 3P) 2RuI (8). The interaction of 3b or 5 with Me 3P=CH 2 leads to the formation of the ylide complex [C 5Me 5(CO)(Me 3P)-RuCH 2PMe 3)Cl (9) or the rutheniumacyl-ylide C 5Me 5(CO) 2RuC(O)CH=PMe 3 (10). 4 reacts with Me 3P=CH 2 to give C 5Me 5(CO)(Me 3P)RuMe (11) and Me 3P via the intermediate formation of the phosphonium salt Me 4P[Ru(CO) (Me 3P)-C 5Me 5]. 相似文献
18.
The chiral bis-imine (1 R,2 R)-C 6H 10-[ E---N=CH---C 6H 3---3,4-(OMe) 2] 2 1 (LH) reacts with [Pd(OAc) 2] (1:1 molar ratio; OAc=acetate) giving the orthometallated [Pd(OAc)( C6H 2---4,5-(OMe) 2---2-CH= N-(1 R,2 R)-C 6H 10--- N=CH---C 6H 3-3′,4′-(OMe) 2-κ-C,N,N)] 2 (abbreviated as [Pd(OAc)(L-κ-C,N,N)]), through C---H bond activation on only one of the aryl rings and N, N-coordination of the two iminic N atoms. 2 reacts with an excess of LiCl to give [Pd(Cl)(L-κ-C,N,N)] 3. The reaction of 3 with AgClO 4 and neutral or anionic ligands L′ (1:1:1 molar ratio) affords [Pd(L-κ-C,N,N)(L′)](ClO 4) (L′=PPh 3 4a, NCMe 5, pyridine 6, p-nitroaniline 7) or [Pd(I)(L-κ-C,N,N)] 8. Complex 4a reacts with wet CDCl 3 giving [Pd( C6H 2---4,5-(OMe) 2---2-CH= N-(1 R,2 R)---C 6H 10--- NH 2-κ-C,N,N)(PPh 3)](ClO 4) 4b as a result of the hydrolysis of the C=N bond not involved in the orthometallated ring. The molecular structure of 4b·CH 2Cl 2 has been determined by X-ray diffraction methods. Cleavage of the Pd---N bond trans to the C aryl atom can be accomplished by coordination of strongly chelating ligands, such as acetylacetonate (acac) or bis(diphenylphosphino)ethane (dppe), forming [Pd(acac- O, O′)(L-κ-C,N)] 9 and [Pd(L-κ-C,N)(dppe-P,P′)](ClO 4) 12, while classical N, N′-chelating ligands such as 1,10-phenantroline (phen) or 2,2′-bipyridyl (bipy) behave as monodentate N-donor ligands yielding [Pd(L-κ-C,N,N)(κ 1-N-phen)](ClO 4) 10 and [Pd(L-κ-C,N,N)(κ 1-N-bipy)](ClO 4) 11. Treatment of 1 with PtCl 2(DMSO) 2 (1:1 molar ratio) in refluxing 2-methoxyethanol gives Cl 2Pt[( NH 2) 2C 6H 10---N,N′] 13a and [Pt(Cl)( C6H 2---4,5-(OMe) 2---2-CH= N-(1 R,2 R)---C 6H 10--- NH 2-κ-C,N,N)] 13b, while [Pt(Cl)(L-κ-C,N,N)] 14 can be obtained by reaction of [Pt(μ-Cl)(η 3-2-Me---C 3H 4)] 2 with 1 in refluxing CHCl 3. Complexes 2 and 3 catalyzed the arylation of methyl acrylate giving good yields of the corresponding methyl cinnamates and TON up to 847 000. Complex 3 also catalyzes the hydroarylation of 2-norbornene, but with lower yields and without enantioselectivity. 相似文献
19.
A study has been carried out of the catalytic activity of the systems formed by [HRh{P(OPh) 3} 4] or [HRh(CO){P(OPh) 3} 3] with the modifying ligands P(OPh) 3, PPh 3, diphos and Cp 2Zr(CH 2PPh 2) 2 in hydroformylation of hex-1-ene (at p = 5 bar). The best results were obtained with the system [HRh{P(OPh) 3} 4]+Cp 2Zr(CH 2PPh 2) 2 (75–85% yeild of aldehydes). 相似文献
20.
Through the oxidation-reduction combination procedure, the neutral tri-substituted {2Fe3S} complex 2 was synthesized by replacing the CO ligand in 1 with phosphine. This substitution leads to the Fe-Fe bonds in 1 and 2 with large Lewis basicity difference, i.e. △pK aMeCN~10. 相似文献
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