共查询到20条相似文献,搜索用时 31 毫秒
1.
D. Carmona S. Chaloupka J. Jans R. Thouvenot L.M. Venanzi 《Journal of organometallic chemistry》1984,275(2):303-313
The preparations of cis- and trans-[PtH(C6Cl5)(PEt3)2] by thermal decomposition of cis- and trans-[Pt(OCHO)(C6Cl5)(PEt3)2], respectively, are reported. Also described are cis- and trans-[Pt(SnCl3)(C6Cl5)(PEt3)2], obtained by treating SnCl2 with cis- and trans-[PtCl(C6,Cl5)(PEt3)2], respectively. It is shown that while trans- [PtH(C6Cl5)(PEt3)2] does not form hydride-bridged complexes in the presence of trans-(PtH(MeOH)(PEt3)2]+, the corresponding complex trans-[PtH(C6)(PEt3)2] reacts with the same solvento complex, in methanol, giving labile [(PEt3)2HPt(-μH)Pt(C6F5)(PEt3)2]+. 相似文献
2.
《Journal of organometallic chemistry》2006,691(1-2):79-85
Trans-[RuCl2(CO)2(PEt3)2] reacts with two equivalents of a series of 1,1-dithiolate ligands to form the bis(dithiolate) complexes, cis-[Ru(CO)(PEt3)(S2X)2] (X = CNMe2, CNEt2, COEt, P(OEt)2, PPh2). Two intermediates have been isolated; trans-[Ru(PEt3)2Cl(CO){S2P(OEt)2}] and trans-[Ru(PEt3)2(CO)(η1-S2COEt)(η2-S2COEt)], allowing a simple reaction scheme to be postulated involving three steps; (i) initial replacement of cis carbonyl and chloride ligands, (ii) substitution of the second chloride, (iii) loss of a phosphine. Thermolysis of cis-[Ru(CO)(PEt3)(S2CNMe2)2] with Ru3(CO)12 in xylene affords trinuclear [Ru3(μ3-S)2(PEt3)(CO)8] as a result of dithiocarbamate degradation. Crystal structures of cis-[Ru(CO)(PEt3)(S2X)2] (X = NMe2, COEt), trans-[Ru(PEt3)2Cl(CO){S2P(OEt)2}], trans-[Ru(PEt3)2(CO)(η1-S2COEt)(η2-S2COEt)] and [Ru3(μ3-S)2(PEt3)(CO)8] are reported. 相似文献
3.
Nigel J. Kermode Michael F. Lappert Brian W. Skelton Allan H. White John Holton 《Journal of organometallic chemistry》1982,228(3):C71-C75
The reaction of [Pt(PEt3)3] with CH2I2 affords trans-[Pt(CH2PEt3)I(PEt3)2]I and is believed to proceed via the α-functionalised alkyl cis-[Pt(CH2I)I(PEt3)2], because similar ylides are obtained from cis- or trans-[PT(CH2X)(PPh3)2X] (XCl, Br, or I) with PR3 (PEt3, PBu3n, PMePh2, PEtPh2, or PPh3); cis-[Pd(CH2I)-I(PPh3)2] does not react with excess PPh3, but with PEt3 yields trans-[Pd(CH2PEt3)I(PPh3)2]I; the X-ray structure of trans-[Pt(CH2PEt3)I(PEt3)2]I (current R = 0.045) shows PtP(1) 2.332(7), PtP(2) 2.341(8), PtC 2.08(2), and PtI 2.666(2) Å, and angles (a) C(1)PtI, P(1), P(2): 176.9(8), 91.6(6), 93.4(6), (b) IPtP(1), P(2): 87.1(2), 88.5(2), and (c) P(1)P(2), 166.8(3), and (d) PtC(1)P(3), 118(1)°. 相似文献
4.
Maxwell A. Cairns Keith R. Dixon Martin A.R. Smith 《Journal of organometallic chemistry》1977,135(1):C33-C34
Syntheses of cis-[PtCl(CH2COCH3)(PEt3)2], cis-[PtCl(CH2NO2) (PEt3)2], and trans-[Pt(CCPh)2 (PEt3)2] are described. The procedure involves reaction of cis-[PtCl2(PEt3)2] with Ag2O and acidic CH bonds to precipitate AgC1 and generate a PtC bond. The method may represent a new general route to platinum—carbon bonds. 相似文献
5.
[Pt(C2O4)(dppe)] reacts thermally with PhCCH to produce [Pt(CCPh)2(dppe)], which has been prepared by alternative routes. Similar treatment of [Pt(C2O4)(dppm)] initially produces [Pt(CCPh)2(dppm)], which rearranges to give cis,cis-[Pt2(CCPh)4(μ-dppm)2]. Reaction of [PtCl2(dppm)] with PhCCH/KOH/18-crown-6, or with (PhCC)SnMe3, gives [Pt(CCPh)2(dppm)], which may be converted to the cis,cis-dimer by addition of oxalic acid. Ultraviolet irradiation or refluxing with a trace amount of dppm converts [Pt(CCPh)2(dppm)] to trans,trans-[Pt2(CCPh)4(μ-dppm)2], but the cis,cis-dimer is stable under these conditions. [Pt(C2O4)L2] (L = PPh3, PEt3) complexes also react thermally with PhCCH to yield [Pt(CCPh)2L2] species. 相似文献
6.
B. Crociani M. Nicolini D.A. Clemente G. Bandoli 《Journal of organometallic chemistry》1973,49(1):249-256
Complexes of the type M(PPh3)2(PbPh3)2 [M = Pd, (Ia) and Pt, (Ib)] have been prepared by oxidative addition of hexaphenyldilead to M(PPh3)4. The compound Pt(PPh3)2(PbPh3)2, (Ib), slowly decomposes in dichloromethane to give cis-Pt(PPh3)2(PbPh3)Ph, (II). which can also be obtained by treating (Ib) with the stoichiometric amount of LiPh. Reaction of Pt(PPh3)4 with hexamethyldidead gives the complex Pt(PPh3)2(PbMe3)Me directly.The MPb bonds are easily cleaved by bromine, iodine and hydrogen bromide. The X-ray structure of (II) has been determined using three-dimensional counter data and refined by the least-square method (R = 0.07). The crystals are monoclinic a = 22.501, b = 10.502, c = 24.120 Å, β = 113.43°, space group P21/c with Z = 4. The complex exhibits a cis configuration, with the coordination around the platinum atom essentially square-planar: the PtPb and PtC(phenyl)bond lengths are 2.698(1) and 2.055(3)Å, respectively. 相似文献
7.
The dimethyl platinum(II) complex containing mixed ligands, cis-[Pt(CH3)2(PEt3)(AsPh3)] reacted with one equivalent of hydrogen chloride yielding trans-[PtCl(CH3)(PEt3)(AsPh3)]. The X-ray crystal structure of the molecule shows the trans orientation of the PEt3 and AsPh3 ligands. 相似文献
8.
《Journal of organometallic chemistry》1987,321(1):123-134
The mixed ligand complexes PtX2(ER3)L and PtXY(ER3)L (where ER3 = PR3 or AsMe3; L = phosphine, arsine; X = Cl; Y = Cl, H or Me) have been prepared and characterized. Reaction of PtMe2(ER3)L with HCl yields PtMeCl(ER3)L, in exclusively one of three possible isomeric forms. Excess tetramethyltin reacts with Pt2Cl2(μ-Cl)2(PMe2Ph)2 giving both cis and trans Pt2(μ-Cl)2(PMe2Ph)2, as identified from the NMR spectra. Cleavage of Pt2(μ-Cl)2Me2(PMe2Ph)2 with donor ligands such as AsPh3, PMe2 or pyridine, was useful as a synthetic route to the unsymmetrical methylchloro PtII derivatives. The reaction of cis-[PtMe2(PPh3)(AsPh3)] with excess dimethylacetylenedicarboxylate (DMA) yielded only one product, which was of the formula trans-[Pt{C(COOCH3)C(COOCH3)CH3}2(PPh3)(AsPh3)], with the alkenyl groups having the same geometry about the CC bond. The use of diethylacetylene-dicarboxylate (DEA) rather than DMA gave a similar product. However, when cis-[PtMe2(PEt3)(AsPh3)] was allowed to react with DMA, two products of the formula trans-[Pt{C(COOCH3)C(COOCH3)CH3}2(PEt3)(AsPh3)] were obtained, with the stereochemistry of both alkenyl groups being either cis or trans. 相似文献
9.
Natalya V. Kirij Ingo Pantenburg Harald Scherer Yurii L. Yagupolskii 《Journal of organometallic chemistry》2006,691(12):2679-2685
The series of cis/trans-trifluoromethylselenato complexes [Pt(SeCF3)2 − xClx(PPh3)2] (x = 0, 1) was identified by NMR spectroscopic methods. While in acetonitrile solution spectra are dominated by the resonances of the cis derivatives, those of pure cis-[Pt(SeCF3)2(PPh3)2] indicate cis-trans-isomerisation in CH2Cl2 solution. In contrast, exchange reactions of cis-[PtCl2(PPh3)2] and [NMe4]TeCF3 only gave evidence for cis isomers. Molecular structures of cis- and trans-[Pt(SeCF3)2(PPh3)2] and cis-[Pt(TeCF3)2(PPh3)2] are discussed in comparison with related compounds. 相似文献
10.
Reactions of the oxorhenium(V) complexes [ReOX3(PPh3)2] (X = Cl, Br) with the N‐heterocyclic carbene (NHC) 1,3,4‐triphenyl‐1,2,4‐triazol‐5‐ylidene (LPh) under mild conditions and in the presence of MeOH or water give [ReOX2(Y)(PPh3)(LPh)] complexes (X = Cl, Br; Y = OMe, OH). Attempted reactions of the carbene precursor 5‐methoxy‐1,3,4‐triphenyl‐4,5‐dihydro‐1H‐1,2,4‐triazole ( 1 ) with [ReOCl3(PPh3)2] or [NBu4][ReOCl4] in boiling xylene resulted in protonation of the intermediately formed carbene and decomposition products such as [HLPh][ReOCl4(OPPh3)], [HLPh][ReOCl4(OH2)] or [HLPh][ReO4] were isolated. The neutral [ReOX2(Y)(PPh3)(HLPh)] complexes are purple, airstable solids. The bulky NHC ligands coordinate monodentate and in cis‐position to PPh3. The relatively long Re–C bond lengths of approximate 2.1Å indicate metal‐carbon single bonds. 相似文献
11.
M. Fernanda N. N. Carvalho Cristina M. C. Laranjeira Antónia T. Z. Nobre Armando J. L. Pombeiro Ana C. A. M. Viegas Raymond L. Richards 《Transition Metal Chemistry》1985,10(11):427-431
Summary Treatment of complexestrans-[M(CNBu-t)2(dppe)2][(1) M = Mo or W, dppe = Ph2PCH2CH2PPh2] with protic acid gives a mixture of the aminocarbyne complexestrans- pluscis-[M(CNHBu-t)(CNBu-t)(dppe)2]+ (2) and the hydridocompounds [MH(CNBu-t)2(dppe)2]+ (3), whereas reaction with an alkylating agent (R+) appears to give the dialkylaminocarbyne compounds [M(CNRBu-t)(CNBu-t)(dppe)2]+ (4) also as a mixture of thetrans andcis isomers. 相似文献
12.
P. Sharma A. Cabrera M. Sharma C. Alvarez J. L. Arias R. M. Gomez S. Hernandez 《无机化学与普通化学杂志》2000,626(11):2330-2334
The work reports the unexpected reaction of diphenyldibromo antimonates (III) with PtCl2 and cis‐[PtCl2(PPh3)2]. The reaction gives triphenylstibine containing PtII complexes viz. cis‐[PtBr2(SbPh3)2] ( 1 ), trans‐[[PtBr(Ph)(SbPh3)2] ( 2 ), [NMe4][PtBr3(SbPh3)] ( 3 ), and cis‐[PtBr2(PPh3)(SbPh3)] ( 4 ). All the complexes were characterised by elemental analyses, IR, Raman, 195Pt NMR, FAB mass spectroscopy and X‐ray crystallography. A plausible mechanism via the phenyl migration is proposed for the formation of these complexes. The average Pt–Br distance in 1 is 2.456(2) Å, in 2 2.496 Å(trans to Ph) while in 3 it is 2.476 Å (trans to Sb) implying a comparable trans influence of Ph3Sb and Ph3P. 相似文献
13.
Elizaveta P. Shestakova Aleksei B. Nikolskii 《Journal of organometallic chemistry》2005,690(14):3397-3404
Cationic methyl complex of rhodium(III), cis-[Rh(Acac)(PPh3)2(CH3)(Py)][BPh4] (1) as a single isomer with Py in the trans to PPh3 position, is formed upon the reaction of cis-[Rh(Acac)(PPh3)2(CH3)(CH3CN)][BPh4] with pyridine in methylene chloride solution.Complex 1 was characterized by elemental analysis and by 31P{1H} and 1H NMR spectra.Cationic pentacoordinate acetyl complexes, trans-[Rh(Acac)(PPh3)2(COCH3)][BPh4] (2) and trans-[Rh(BA)(PPh3)2(COCH3)][BPh4] (3), are prepared by action of carbon monoxide on cis-[Rh(Acac)(PPh3)2(CH3)(CH3CN)][BPh4] and cis-[Rh(BA)(PPh3)2(CH3)(CH3CN)][BPh4], respectively, in methylene chloride solutions.Complexes 2 and 3 were characterized by elemental analysis and by IR, 31P{1H}, 13C{1H} and 1H NMR. According to NMR data, 2 and 3 in solution are non-fluxional trigonal bipyramids with β-diketonate and acetyl ligands in the equatorial plane and axial phosphines.In solutions, 2 and 3 gradually isomerize into octahedral methyl carbonyl complexes trans-[Rh(Acac)(PPh3)2(CO)(CH3)][BPh4] (4) and trans-[Rh(BA)(PPh3)2(CO)(CH3)][BPh4] (5), respectively.Complexes 4 and 5 were characterized by IR, 31P{1H}, 13C{1H} and 1H NMR, without isolation.Upon the action of PPh3 on cis-[Rh(Acac)(PPh3)2(CH3)(CH3CN)][BPh4] and cis-[Rh(BA)(PPh3)2(CH3)(CH3CN)] [BPh4], reductive elimination of the methyl ligand as a phosphonium salt, [CH3PPh3][BPh4], occurs to give square planar rhodium(I) complexes [Rh(Acac)(PPh3)2] and[Rh(BA)(PPh3)2], respectively. The reaction products were identified in the reaction mixtures by 31P{1H} and 1H NMR. 相似文献
14.
The reactions of aminophosphines with Group 6 metal carbonyls afford both mono-substituted and disubstituted complexes. The reaction of Ph2PN(H)C6H11 with molybdenum tetracarbonyl derivative gives a mixture of cis and trans-isomers. The reaction of Ph2PN(H)Ph with Pd(COD)Cl2 leads to the PN bond cleavage to give chloro bridged dimer, [Pd(PPh2O)(PPh2OH)(μ-Cl)]2, whereas with Pt(COD)Cl2, disubstituted cis-[PtCl2{PPh2N(H)R}2]2 was obtained. The reaction of Ph2PN(H)C6H11 with RuCl2(DMSO)4 or RuCl2(PPh3)3 leads to the formation of ionic complex, [RuCl{Ph2PN(H)C6H11}3]Cl. 相似文献
15.
Renzo Ross Rino A. Michelin Raymond Bataillard Raymond Roulet 《Journal of organometallic chemistry》1978,161(1):75-90
Reactions of the PtH and/or PtC bonds of the hydridocyanoalkyl complexes cis- or trans-PtH[(CH2)nCN]L2 (n = 1, 3; L2 = 2 PPh3, Ph2PCHCHPPh2) are described, viz. reductive elimination induced by CO, PhCCPh, PEt3, PPhMe2, cis-Ph2PCHCHPPh2 to give Pt(CO)2L2, PtL2(PhCCPh), PtL2, PtL(PPhMe2)3, PtL2(Ph2PCHCHPPh2) (L = PPh3), respectively, and cleavages by acids, halogens and alkyl halides.The monomeric hydroxo complexes cis-Pt(OH)[(CH2)nCN]L2 were shown to be intermediates in the synthesis of PtH[(CH2)nCN]L2 from cationic cyanoalkyl complexes in alcoholic NaOH. Their characterisation and the reactions of the PtOH bond with activated methyl groups are reported. 相似文献
16.
D. Carmona R. Thouvenot L.M. Venanzi F. Bachechi L. Zambonelli 《Journal of organometallic chemistry》1983,250(1):589-608
The mono-hydrido-bridged complexes (PEt3)2(Ar)Pt(μ2-H)Pt(Ar)(PEt3)2]-[BPh4] (Ar = Ph, 4-MeC6H4 and 2,4-Me2C6H3) have been obtained by treating trans-[Pt(Ar)(MeOH)(PEt3)2][BF4] with sodium formate and Na[BPH4]. The cations [PEt3)2(Ar)Pt(μ2-H)Pt(Arb')(PEt3)2]b+ (Ar = Ph and Arb' - 2,4-Me2C6H3 and 2,4,6-Me3C6H2 have bee identified in solution. Their b1H- and b31P-NMR data are reported. The X-ray crystal structure of [(PEt3)2(Ph)Pt(μ2-H)Pt(Ph)(PEt3)2][BPh4] is reported. 相似文献
17.
《Journal of organometallic chemistry》1986,314(3):369-383
Among the several hydrides formed when trans-[PtHClL2] (L = PPh3) reacts with Sncl2, only trans-[PtH(SnCl3)L2] rapidly inserts ethylene, at −80°C, to yield cis-[PtEt(SnCl3)L2]. At −10°C, cis-[PtEt(SnCl3)L2] irreversibly rearranges to the trans-isomer, thus indicating that the cis-isomer is the kinetically controlled species, and that the trans-isomer is thermodynamically more stable.At −50°C, a mixture of trans-[PtHClL2] and trans[PtH(SnCl3)L2] reacts with ethylene to give cis-[PtEtClL2] and cis-[PtEt(SnCl3)L2] and this has been attributed to the catalytic activity of SnCl2 which dissociates from cis-[PtEt(SnCl3)L2] at this temperature.Carbon monoxide promotes the cis-trans isomerization of cis[PtEt(SnCl3)L2], which occurs rapidly even at −80°C. This rearrangement is followed by a slower reaction leading to the cationic complex trans-[PtEt(CO)L2]+ SnCl3−. At −80°C, this complex does not react further, but when it is kept at room temperature ethyl migration to coordinated carbon monoxide takes place, to give several Pt-acyl complexes, i.e. trans-[PtCl(COEt)L2], trans-[Pt(SnCl3)(COEt)L2], trans-[PtCl(COEt)l2 · SnCl2], and trans-[Pt(COEt)(CO)L2]+ SnCl3−. This mixture of Pt-acyl complexes reacts with molecular hydrogen to yield n-propanal and the same complex mixture of platinum hydrides as is obtained by treating trans-[PtHClL2] with SnCl2.Trans-[PtH(SnCl3)L2] reacts with carbon monoxide to yield the five-coordinate complex [PtH(SnCl3)(CO)2L2], which has been characterized by NMR and Ir spectroscopy; ethylene does not insert into the PtH bond of this complex at low temperature. At room temperature, trans-[PtH(SnCl3)L2] reacts with a mixture of CO and ethylene to yield the same mixture of Pt-acyl species as is obtained when trans-[PtEt(SnCl3)L2] is allowed to react with CO.The role of a PtSn bond in these reactions is discussed in relation to the catalytic cycle for the hydroformylation of olefins. 相似文献
18.
Elizaveta P. Shestakova Konstantin A. Lyssenko Viktor N. Khrustalev 《Journal of organometallic chemistry》2004,689(11):1930-1943
Cationic methyl complex of rhodium(III), trans-[Rh(Acac)(PPh3)2(CH3)(CH3CN)][BPh4] (1) is prepared by interaction of trans-[Rh(Acac)(PPh3)2(CH3)I] with AgBPh4 in acetonitrile. Cationic methyl complexes of rhodium(III), cis-[Rh(Acac)(PPh3)2 (CH3)(CH3CN)][BPh4] (2) and cis-[Rh(BA)(PPh3)2(CH3)(CH3CN)][BPh4] (3) (Acac, BA are acetylacetonate and benzoylacetonate, respectively), are obtained by CH3I oxidative addition to rhodium(I) complexes [Rh(Acac)(PPh3)2] and [Rh(BA)(PPh3)2] in acetonitrile in the presence of NaBPh4. Complexes 2 and 3 react readily with NH3 at room temperature to form cis-[Rh(Acac)(PPh3)2(CH3)(NH3)][BPh4] (4) and cis-[Rh(BA)(PPh3)2(CH3)(NH3)][BPh4] (5), respectively. Complexes 1-5 were characterized by elemental analysis, 1H and 31P{1H} NMR spectra. Complexes 1, 2, 3 and 4 were characterized by X-ray diffraction analysis. Complexes 2 and 3 in solutions (CH2Cl2, CHCl3) are presented as mixtures of cis-(PPh3)2 isomers involved into a fluxional process. Complex 2 on heating in acetonitrile is converted into trans-isomer 1. In parallel with that isomerization, reductive elimination of methyl group with formation of [CH3PPh3][BPh4] takes place. Replacement of CH3CN in complexes 1 and 2 by anion I− yields in both cases the neutral complex trans-[Rh(Acac)(PPh3)2(CH3)I]. Strong trans influence of CH3 ligand manifests itself in the elongation (in solid) and labilization (in solution) of rhodium-acetonitrile nitrogen bond. 相似文献
19.
The facile access to the Vaska type fluorido complexes trans-[Ir(F)(CO)(PR3)2] [ 6 : R = Et, 7 : R = Ph, 8 : R = iPr, 9 : R = Cy, 10 : R = tBu] was achieved by halide exchange at trans-[Ir(Cl)(CO)(PR3)2] ( 1 – 5 ) with Me4NF. Furthermore, the reaction of complex 6 with SF4 gave cis,trans-[Ir(F)2(SF3)(CO)(PEt3)2] ( 11 ), whereas 8 – 10 did not react. Reactivity studies revealed that 11 can selectively be manipulated at the sulfur atom by hydrolysis or fluoride abstraction to give cis,trans-[Ir(F)2(SOF)(CO)(PEt3)2] ( 12 ) and cis,trans-[Ir(F)2(SF2)(CO)(PEt3)2][AsF6] ( 13 ), respectively. 相似文献
20.
David A. Clarke Martin M. Hunt Raymond D.W. Kemmitt 《Journal of organometallic chemistry》1979,175(2):303-313
Reactions of alloxan (all) with [PtL(PPh3)2] (L′= -stilbene, L″ diphenylacetylene) afford the side-bonded ketone complex [Pt(all)(PPh3)2] which may also be obtained from the hydrate of alloxan and [PtL′(Pph3)2]. Similarly diethyl oxomalonate (dio) and [Pt(PPh3)4] afford a side-bonded ketone complex [Pt(dio)(PPh3)2]. Reaction of isatin with [Pt(PPh34] gives -[PtH{}(PPh3)2] and benzoyl cyanide and [PtL′(PPh3)2] give -[Pt(CN)(COPh3)2] and -[Pt(CN)2(PPh2)2]. 相似文献