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1.
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
2.
Nisha P. Kushwah Amey Wadawale Zoya A. Starikova 《Journal of organometallic chemistry》2009,694(26):4146-4263
The reactions of [M2Cl2(μ-Cl)2(PMe2Ph)2] with mercapto-o-carboranes in the presence of pyridine afforded mono-nuclear complexes of composition, [MCl(SCb°R)(py)(PMe2Ph)] (M = Pd or Pt; Cb° = o-C2B10H10; R = H or Ph). The treatment of [PdCl2(PEt3)2] with PhCb°SH yielded trans-[Pd(SCb°Ph)2(PEt3)2] (4) which when left in solution in the presence of pyridine gave another substitution product, [Pd(SCb°Ph)2(py)(PEt3)] (5). The structures of [PdCl(SCb°Ph)(py)(PMe2Ph)] (1), [Pd(SCb°Ph)2(PEt3)2] (4) and [Pd(SCboPh)2(py)(PEt3)] (5) were established unambiguously by X-ray crystallography. The palladium atom in these complexes adopts a distorted square-planar configuration with neutral donor atoms occupying the trans positions. Thermolysis of [PdCl(SCb°)(py)(PMe2Ph)] (2) in TOPO (trioctylphosphine oxide) at 200 °C gave nanocrystals of TOPO capped Pd4S which were characterized by XRD pattern and SEM. 相似文献
3.
John R. Briggs Christopher Crocker Walter S. McDonald Bernard L. Shaw 《Journal of organometallic chemistry》1979,181(1):213-221
Five complexes of type cis-[PtCl2(PR3)Q] (PR3 =PMe3, PMe2Ph, PEt3; Q = CH2 CHOCOCH3 or CH2=CHCH2OCOCH3) have been prepared. The crystal structure of cis-[PtCl2[PME2Ph)(CH2=CHOCOCH3)] is described. Crystals of cis-[PtCl2(PME2Ph)(CH2-CHOCOCH3)] are triclinic, with a 8.441(4), b 13.660(5), c 7.697(3) Å, a 101.61(3)°, β 111.85(3)° γ 95.22(3)°, pP1, Z = 2. The structure was determined from 2011 reflections I σ 3σ (I) and refined to R = 0.037. The CH3COO grouping is syn to the cis-PMe2Ph ligand, with bond lengths of PtCl (trans to P) 2.367(3), PtCl (trans to olefin) 2.314(3), PtP 2.264(2), and PtC of 2.147(12) and 2.168(11) Å. The complexes cis-[PtCl2- (PR3)Q] were studied by variable temperature 1H and 31P NMR spectroscopy. Spectra of the vinyl acetate complexes were temperature dependent as a result of rotation about the platinum—olefin bond. The rotation was “frozen out” at ca. 240 K; for cis-[PtCl2(PME2Ph)(CH2=CHOCOCH3] ΔG≠ (rotation) 15.0 ± 0.2 kcal mol-1. NMR parameters for the rotamers are reported. NMR studies of the interaction between chloro-bridged complexes of type [Pt2Cl2(PR3)2] (PR3 = P-N-Pr3 or PMe2Ph) and vinyl acetate shows that even at low temperatures (213 K) equilibrium favours the bridged complex and the proportion of trans-[PtCl2(PR3)CH2=CHOCOCH3)] is very small e.g. 2%. The allyl acetate complexes cis-[PtCl2(PR3)(CH2=CHCH2OCOCH3)] showed only one rotamer over the range 333–213 K. Reversible dissociation of cis-[PtCl2(PMe2Ph)- (CH2=CHCH2OCOCH3)] to [Pt2Cl4(PMe2Ph)2] + allyl acetate was studied at ambient temperature. At low temperatures e.g. 213–190 K addition of allyl acetate to a CDCl3 solution of [Pt2Cl2(P-n-Pr3)2] reversibly gave some olefin complex trans-[PtCl2(P-n-Pr3)(CH2=CHCH2OCOCH3)] and some O-bonded complex trans-[PtCl2(P-n-Pr3)(CH2=CHCH2OCOCH3)]. 相似文献
4.
R. Contreras G.G. Elliot R.O. Gould G.A. Heath A.J. Lindsay T.A. Stephenson 《Journal of organometallic chemistry》1981,215(1):C6-C10
Several isomers of the type [M2Cl5L4] (M = Ru, L = AsPh3, As(p-tol)3, As(p-PhCl)3, PEt2Ph, PMe2Ph; L2 = Ph2As(CH2)2AsPh2; M = Os, L = PPh3, AsPh3) have been synthesised by various routes and characterised by magnetic, ESR and electrochemical measurements, and for [(PEt2Ph)Cl2RuCl3Ru(PEt2Ph)3] by X-ray structural analysis. 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.
Talal A.K. Al-Allaf Gregory Butler Colin Eaborn Alan Pidcock 《Journal of organometallic chemistry》1980,188(3):335-343
The complex [Pt(C2H4)(PPh3)2] reacts with Pb2Ph6 to give cis-[PtPh(Pb2Ph5)(PPh3)2]; this decomposes in solution to cis-[PtPh(PbPh3)(PPh3)2], which may also be obtained from the ethylene complex and PbPh4. Lead compounds PbPhMe3 and PbPh3Br also give products of insertion into PbPh bonds, but PbMe3Cl gives cis- and trans-[PtCl(PbMe3)(PPh3)2]. The complex trans-[Pt(PbPh3)2(PEt3)2] reacts with 1,2-bis(diphenylphosphino)ethane (DPPE) to give [Pt(PbPh3)2(DPPE)] which readily decomposes in dichloromethane in presence of PEt3 to give [Pt(PbPh3)(PEt3)(DPPE)]Cl and [PtPh(PEt3)(DPPE)]Cl. The complex trans-[PtCl(PbPh3)(PEt3)2] was detected in the products of reactions between trans-[PtCl2(PEt3)2] and trans-[Pt(PbPh3)2(PEt3)2] or less than 2 moles of LiPbPh3; it was not detected in the mixture after treatment of trans -[Pt(PbPh3)2(PEt3)2] with HCl. In contrast to an earlier report, we were unable to detect lead-containing complexes in the products of the reaction between trans-[PtHCl(PPh3)2] and Ph3PbNO3. The complexes and their decomposition products were identified by pre31P-{1H} NMR spectroscopy. 相似文献
7.
The reduction of trans-RuCl2(PMe3)4 with Na/Hg and of trans-OsCl2(PMe3)4 with sodium in the presence of catalytic amounts of naphthalene gives the complexes RuH(η2-CH2PMe2)(PMe3)3 (III) and OsH(η2-CH2PMe2PMe2), (IV) in good yields. An equilibrium with the metal(0) isomers [M(PMe3)4] cannot be detected by NMR spectroscopy. III and IV react with dihalomethanes CH2X2 (X = Cl, Br, I) and CH3I to form mixtures of the dimethylphosphinomethanide complexes MX(η2-CH2PMe2)(PMe3)3 and the compounds MX2(PMe3)4. The reactions of III and IV with the Brönsted acids HCl, HBr, CF3CO2H and HC2Ph lead (with exception of M = Ru and X = C2Ph) to the complexes cis-MX2(PMe3)4. The hydrolysis of IV gives the hydrido(hydroxy) compound cis-OsH(OH)(PMe3)4, which has been characterized by 1H, 31P NMR and mass spectroscopy. The synthesis of the complex cis-Os(CH3)2(PMe3)4 is also described; the conversion into the ethylene(hydrido)metal cation [OsH(C2H4)(PMe3)4]+ failed. 相似文献
8.
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
9.
The symmetrisation reaction between cis-[PtMe2 (PMe2Ph)2] and cis-[PtCl2-(PMe2Ph)2] to give cis-[PtClMe(PMe2Ph)2] is catalysed by [Pt2Cl2 (μ-Cl)2-(PMe2Ph)2]. 相似文献
10.
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
11.
The complexes [ReCl(N2)(PMe2Ph)jtJ. Amer. Chem. Soc.43] and [ReCl(N2)(PMe2Ph)3(pyridine)] react with organic acid halides, RCOCl, to form acylazo- and aroylazo-complexes, [ReCl2(N2COR)(PMe2Ph)3], for which X-ray diffraction studies confirm the formation of the NC bond; the osmium complex [OsCl2(N2)(PEt2Ph)3] does not undergo analogous reactions. 相似文献
12.
《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
13.
《Journal of organometallic chemistry》1987,323(1):C10-C12
[Ru(CO)4PMe3] reacts with MeI to give fac-[Ru(CO)3(PMe3)(Me)I]. The latter reacts with PMe3 to give a mixture of the three isomers of cis-bis(trimethylphosphine)-cis-dicarbonyl acetyl iodide [Ru(CO)2(PMe3)2(COMe)I]. Decarbonylation of the mixture gives only the trans-bis(trimethylphosphine)-cis-dicarbonyl methyl iodide complex [Ru(CO)2(PMe3)2MeI], which was also prepared by oxidative addition of MeI to [Ru(CO)3(PMe3)2]. 相似文献
14.
《Journal of organometallic chemistry》1986,310(1):127-134
[Pd2(μ-Cl)2Cl2L2] (L = PEt3, PBu3 or PMe2Ph) reacts with AlMe3 in ether, THF or a mixture of these solvents depending on L to give [Pd2(μ-Cl)2Me2L2] in high yield, which has been characterized by IR and NMR spectroscopy as well as elemental analysis. Treatment of [Pd2(μ-Cl)2Me2L2] with CO yields [Pd2(μ-Cl)2(COMe)2L2], while its reaction with L leads to trans-[PdClMeL2]. The preparative method and the characteristic data of these complexes are discussed in comparison with the earlier work on the analogous aryl and aralkyl complexes. 相似文献
15.
J. Dehand A. Mauro H. Ossor M. Pfeffer R.H. de A. Santos J.R. Lechat 《Journal of organometallic chemistry》1983,250(1):537-550
Treatment of 1-methoxynaphthalene (MXNH) with n-butyllithium in a diethyl ether/n-hexane solution gives 1-methoxynaphthalene-8-lithium (MXNLi) in 30% yield as an insoluble material. This compound reacts with PdCl2(SEt2)2 to give bis(1-methoxynaphthalene-8-C,O)palladium(II) (I)_and with PtCl2(SEt2)2 to give cis- and trans-(1-methoxynaphthalene-8-C,O)(1-methoxynaphthalene-8-C)(diethylsulfide)platinum(II) (II), which are non-rigid molecules in solution. With the cyclopalladated dimers [{)Cl2}2], MXNLi gives the palladobicyclic compounds: () (III). An X-ray diffraction study of compound IIIa where N∩N = 8-methylquinoline-C,N reveals the planarity of the molecule, shows that it has a cis configuration with respect to the PdC bonds, and confirms that the oxygen atom of MXN is bonded to palladium: PdO 2.236(4) Å. The geometry of IIIa is maintained in solution, whereas the corresponding compounds IIIb and IIIc in which N∩C is benzo[h]quinoline-9-C,N and N,N-dimethyl-1-naphthylamine-8-C,N, respectively, appear to be mixtures of cis and trans isomers in solution. With PMe2Ph I and II give trans-Pd(MXN)2(PMe2Ph)2 and cis-Pt(MNX)2(PMe2Ph)2, respectively, in which the methoxynaphthalene is bound to the metals via the 8-carbon of the naphthalene ring. Only one phosphine ligand adds to compounds IIIb and IIIc with displacement of the O → Pd bond. One carbon monoxide ligand can be added to the platinum compound II to give Pt(MXN)2(SEt2)CO which in solution exists as two isomers in equilibrium. 相似文献
16.
Bruno Crociani Francesca Dibianca Amalia Giovenco Alberto Scrivanti 《Journal of organometallic chemistry》1985,291(2):259-272
The oxidative addition of 2-chloropyrimidine or 2-chloropyrazine to [Pd(PPh3)4] yields a mixture of trans-[PdCl(C4H3N2-C2)(PPh3)2] (I) and [PdCl(μ-C4H3N2-C2,N1)(PPh3 (II) (C4H3N2 = 2-pyrimidyl or 2-pyrazyl group). The mononuclear complexes I are quantitatively converted into the binuclear species II upon treatment with H2O2. The reaction of II with HCl gives the N-monoprotonated derivatives cis-[PdCl2(C4H4N2-C2)(PPh3)] (III), from which the cationic complexes trans-[PdCl(C4H4N2-C2)(L) (L = PPh3, IV; PMe2Ph, V; PEt3, VI) can be prepared by ligand substitution reactions. Reversible proton dissociation occurs in solution for III–VI. The low-temperature 1H NMR spectra of trans-[PdCl(C4H4N2-C2)(PMe2Ph)2]ClO4 show that the heterocyclic moiety undergoes restricted rotation around the PdC2 bond and that the 2-pyrazyl group is protonated predominantly at the N1 atom. These results and the 13C NMR data for the PEt3 derivatives are interpreted on the basis of a significant dπ → π★ back-bonding contribution to the palladium—carbon bond of the protonated ligands. 相似文献
17.
Donald S. Matteson 《Journal of organometallic chemistry》1975,101(1):C17-C18
Methyl iodide reacts with Pt2(μ-SMe)2Ph2(PMe2Ph)2 to give PtIPh(SMe2)(PMe2Ph) and with Pt2(μ-SMe)2Me2(PMe2Ph)2 to give PtI2Me2(SMe2)(PMe2Ph) via an isolable intermediate Pt2I2(μ-SMe)2Me4(PMe2Ph)2. The mechanisms of the reactions are discussed. 相似文献
18.
Manoj K. Pal Nisha P. Kushwah Sergey A. Glazun Vladimir I. Bregadze 《Journal of organometallic chemistry》2010,695(24):2629-2634
The reactions of PhCboSeNa (Cbo = o-C2B10H10), prepared by reductive cleavage of Se-Se bond in (PhCboSe)2 by NaBH4 in methanol, with Na2PdCl4, MCl2(PR3)2 and [M2Cl2(μ-Cl)2(PR3)2] afforded a variety of complexes, viz., [Pd(SeCboPh)Cl] (1), [M(SeCboPh)2(PR3)2], [M2Cl2(μ-SeCboPh)(μ-Cl)(PR3)2] (M = Pd, Pt) and [Pd2Cl(SeCb0Ph)(μ-Cl)(μ-SeCboPh)(PEt3)2] (7) have been isolated. These complexes were characterized by elemental analyses and NMR (1H, 31P, 77Se, 195Pt) spectroscopy. The structures of [Pd(SeCboPh)2(PEt3)2] (2), [Pt(SeCboPh)2(PMe2Ph)2] (3), [Pd2Cl2(μ-SeCboPh)(μ-Cl)(PMe2Ph)2] (5) and [Pd2Cl(SeCboPh)(μ-Cl)(μ-SeCboPh)(PEt3)2] (7) were established by X-ray crystallography. The latter represents the first example of asymmetric coordination of selenolate ligands in binuclear bis chalcogenolate complexes of palladium and platinum. Thermolysis of [Pd(SeCboPh)2(PEt3)2] (2) in HDA (hexadecylamine) at 330 °C gave nano-crystals of Pd17Se15. 相似文献
19.
A number of neutral, mononuclear dialkylpalladium(II) tertiary phosphine complexes of geneal formula cis or trans-PdR2(PMe3)2 and cis-PdR2 (dmpe) [dmpe = 1,2-bis(dimethylphosphino)ethane], R = Me, CH2Ph, CH2CMe2Ph, CH2SiMe3 have been obtained by interaction of magnesium reagents with palladium(II) acetate or trans-Pd(O2CMe)2(PMe3)2. 相似文献
20.
Ernesto Carmona Jose M. Marin Manuel L. Poveda Robin D. Rogers Jerry L. Atwood 《Journal of organometallic chemistry》1982,238(4):C63-C66
The reduction of [WCl4(PMe3)3] with dispersed sodium, under dinitrogen, gives cis-[W(N2)2(PMe3)4], while under ethylene trans-[W(C2H4)2(PMe3)4] is obtained. The ethylene complex can also be prepared by displacement of the dinitrogen molecules in cis-[W(N2)2(PMe3)4] by ethylene at room temperature and pressure. Interaction of cis-[M(N2)2(PMe3)4] complexes (M = Mo, W), with PMe3, under helium or argon, yields [M(N2)(PMe3)5]. The molybdenum complex crystallizes in the orthorhombic space group Pnma, with a 22.063(6), b 12.106(4), c 9.745(4) Å. The Mo—P distance trans to the dinitrogen ligand (2.483(7) Å) is slightly longer than the average of the other four Mo—P bonds (2.460(5) Å). 相似文献