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1.
[reaction: see text]. Catalysis of the glyoxylate-ene reaction by dicationic P2Pt(II) complexes is subject to anion-dependent additive effects. For [((S)-MeOBiphep)Pt](OTf)2 catalysts, acidic phenols such as 3-CF3-C6H3OH or C6F5OH provide substantial rate increases but do not affect the more active SbF6-based catalysts. Enantioselectivity and reactivity also increased with diphosphine basicity, with 4-t-Bu-substituted MeOBiphep ligands yielding the highest enantioselectivities. 相似文献
2.
Thomas CM Mafua R Therrien B Rusanov E Stoeckli-Evans H Süss-Fink G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(15):3343-3352
The new diphosphine ligands Ph(2)PC(6)H(4)C(O)X(CH(2))(2)OC(O)C(6)H(4)PPh(2) (1: X=NH; 2: X=NPh; 3: X=O) and Ph(2)PC(6)H(4)C(O)O(CH(2))(2)O(CH(2))(2)OC(O)C(6)H(4)PPh(2) (5) as well as the monophosphine ligand Ph(2)PC(6)H(4)C(O)X(CH(2))(2)OH (4) have been prepared from 2-diphenylphosphinobenzoic acid and the corresponding amino alcohols or diols. Coordination of the diphosphine ligands to rhodium, iridium, and platinum resulted in the formation of the square-planar complexes [(Pbond;P)Rh(CO)Cl] (6: Pbond;P=1; 7: Pbond;P=2; 8: Pbond;P=3), [(Pbond;P)Rh(CO)Cl](2) (9: Pbond;P=5), [(P-P)Ir(cod)Cl] (10: Pbond;P=1; 11: Pbond;P=2; 12: Pbond;P=3), [(Pbond;P)Ir(CO)Cl] (13: Pbond;P=1; 14: Pbond;P=2; 15: Pbond;P=3), and [(Pbond;P)PtI(2)] (18: Pbond;P=2). In all complexes, the diphosphine ligands are trans coordinated to the metal center, thanks to the large spacer groups, which allow the two phosphorus atoms to occupy opposite positions in the square-planar coordination geometry. The trans coordination is demonstrated unambiguously by the single-crystal X-ray structure analysis of complex 18. In the case of the diphosphine ligand 5, the spacer group is so large that dinuclear complexes with ligand 5 in bridging positions are formed, maintaining the trans coordination of the P atoms on each metal center, as shown by the crystal structure analysis of 9. The monophosphine ligand 4 reacts with [[Ir(cod)Cl](2)] (cod=cyclooctadiene) to give the simple derivative [(4)Ir(cod)Cl] (16) which is converted into the carbonyl complex [(4)Ir(CO)(2)Cl] (17) with carbon monoxide. The crystal structure analysis of 16 also reveals a square-planar coordination geometry in which the phosphine ligand occupies a position cis with respect to the chloro ligand. The diphosphine ligands 1, 2, 3, and 5 have been tested as cocatalysts in combination with the catalyst precursors [[Rh(CO)(2)Cl](2)] and [[Ir(cod)Cl](2)] or [H(2)IrCl(6)] for the carbonylation of methanol at 170 degrees C and 22 bar CO. The best results (TON 800 after 15 min) are obtained for the combination 2/[[Rh(CO)(2)Cl](2)]. After the catalytic reaction, complex 7 is identified in the reaction mixture and can be isolated; it is active for further runs without loss of catalytic activity. 相似文献
3.
Marx T Wesemann L Dehnen S Pantenburg I 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(14):3025-3032
Three stannaborate complexes of platinum(II) and a novel stannoborate palladium(II) derivative have been prepared in excellent yield. The tin transition metal bond is formed through nucleophilic substitution and the resulting complexes [Bu3MeN] [trans-[(Et3P)2Pt(SnB11H11)H]] (6), [trans-[(Et3P)2Pt(SnB11H11)(CNtBu)]] (7), [Bu3MeN]2[trans-[(Et3P)2Pt(SnB11H11)2-(CNtBu)]] (8), and [Bu3MeN][(dppe)-Pd(SnB11H11)Me] (12) (dppe = 1,2-bis-(diphenylphosphanyl)ethane) were characterized by NMR spectroscopy and elemental analysis. In the cases of the zwitterion 7, the pentacoordinated complex 9, the palladium salt 12 and [(triphos)Pt(SnB11H11)] (10) (triphos = 1,1,1-tris(diphenylphosphanylmethyl)ethane), their solid-state structures are determined by X-ray crystal structure analyses. The trans influence of the [SnB11H11] ligand is evaluated from the results of the IR spectroscopy and X-ray crystallographic structures of complexes 6, 7, and 12. The dipole moment of the zwitterion 7 is calculated by density functional theory (DFT) methods. The alignment of the dipole moments of the polar molecules 7 and 12 in the solid state is discussed. 相似文献
4.
Crespo O Gimeno MC Jones PG Laguna A López-de-Luzuriaga JM Monge M Pérez JL Ramón MA 《Inorganic chemistry》2003,42(6):2061-2068
The free nido-diphosphine anions [(PR(2))(2)C(2)B(9)H(10)](-) (R = Ph, (i)Pr) show luminescence properties whereas the closo-diphosphines [(PR(2))(2)C(2)B(10)H(10)] do not. Four families of three-coordinate complexes of stoichiometry [Au[(PR(2))(2)C(2)B(10)H(10)]L]OTf (L = tertiary phosphine) and [Au[(PR(2))(2)C(2)B(9)H(10)]L] have been studied in order to analyze the influence of the closo- or nido-nature of the diphosphine, the monophosphine coordinated to gold and the substituent at the diphosphine on the luminescence of the complexes. Only the nido-derivatives show luminescence. The maxima of the emissions are shifted to lower energies than those of the corresponding free nido-diphosphines. When the substituent at the diphosphine is phenyl, a new emission appears, which has been assigned as arising from a metal to ligand charge transfer [Au-->pi(L)] excited state. 相似文献
5.
Pattacini R Margraf G Messaoudi A Oberbeckmann-Winter N Braunstein P 《Inorganic chemistry》2008,47(21):9886-9897
The heterocycles 2-methyl-2-oxazoline (mox) and 2-methyl-2-thiazoline (mth) react with Ph2PCl under mild conditions, in the presence of NEt3 which promotes their phosphorylation by stabilization of their enamino tautomers mox(e) and mth(e), respectively, and which also behaves as HCl scavenger. Depending on the reaction conditions, three different phosphine ligands were obtained in good yields from mox: the monophosphine Ph2PCH2C=NCH2CH2O (1ox) and the isomeric diphosphines Ph2PCH=COCH2CH2NPPh2 (2ox) (X-ray structure) and (Ph2P)2CHC=NCH2CH2O (3ox). The formation of these ligands involves phosphoryl migration reactions, which were studied by NMR spectroscopy. The synthesis and the X-ray structures of the corresponding diphenylphosphinothiazolines Ph2PCH2C=NCH2CH2S (1th) and Ph2CH=CSCH2CH2NPPh2 (2th) are also reported but the thiazoline analog of the geminal diphosphine 3ox was not observed. The metal complexes [Pt(3ox-H)2] x 4 CH2Cl2 (4 x 4 CH2Cl2), [Pt(Me)I(1ox)] (5), [Pt(Me)2(1ox)] (7), [Pd(dmba-C,N)(1th)]OTf x 0.25 Et2O (8 x 0.25 Et2O), [Pd(dmba-C,N)(1th-H)] (9), and [9 x {Pd(dmba-C,N)Cl}] x 2.5 C6H6 (10 x 2.5 C6H6) have been prepared and structurally characterized by X-ray diffraction. 相似文献
6.
Ruwwe J Martín-Alvarez JM Horn CR Bauer EB Szafert S Lis T Hampel F Cagle PC Gladysz JA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(18):3931-3950
The broad applicability of the title reaction is established through studies of neutral and charged, coordinatively saturated and unsaturated, octahedral and square planar rhenium, platinum, rhodium, and tungsten complexes with cyclopentadienyl, phosphine, and thioether ligands which contain terminal olefins. Grubbs' catalyst, [Ru(=CHPh)(PCy3)2(Cl)2], is used at 2-9 mol% levels (0.0095-0.00042 M, CH2-Cl2). Key data are as follows: [(eta5-C5H4(CH2)6CH=CH2)Re(NO)(PPh3)-(CH3)], intermolecular metathesis (95 %); [(eta5-C5H5)Re(NO)(PPh3)(E(CH2CH=CH2)2)]+ TfO (E=S, PMe, PPh), formation of five-membered heterocycles (96-64%; crystal structure E = PMe); [(eta5-C5Me5)Re(NO)(PPh((CH2)6CH=CH2)2)(L)]n+ nBF4-(L/n = CO/1, Cl/0), intramolecular macrocyclization (94-89%; crystal structure L= Cl); fac-[(CO)3Re(Br)(PPh2(CH2)6CH=CH2)2] and cis-[(Cl)2Pt(PPh2(CH2)6CH=CH2)2], intramolecular macrocyclizations (80-71%; crystal structures of each and a hydrogenation product); cis-[(Cl)2Pt(S(R)(CH2)6CH= CH2)2], intra-/intermolecular macrocyclization (R=Et, 55%/24%; tBu, 72%/ <4%); trans-[(Cl)(L)M(PPh2(CH2)6CH=CH2)2] (M/L = Rh/CO, Pt/C6F5) intramolecular macrocyclization (90-83%; crystal structure of hydrogenation product, M=Pt); fac-[W(CO)3(PPh((CH2)6CH=CH2)2)3], intramolecular trimacrocyclization (83 %) to a complex mixture of triphosphine, diphosphine/ monophosphine, and tris(monophosphine) complexes, from which two isomers of the first type are crystallized. The macrocycle conformations, and basis for the high yields, are analyzed. 相似文献
7.
Calhorda MJ Crespo O Gimeno MC Jones PG Laguna A López-de-Luzuriaga JM Perez JL Ramón MA Veiros LF 《Inorganic chemistry》2000,39(19):4280-4285
Treatment of the tetranuclear gold cluster [Au4((PPh2)2C2B9H10)2(AsPh3)2] (1), which contains the nido-carborane-diphosphine [7,8-(PPh2)2C2B9H10]-, with various tertiary phosphines leads to derivatives [Au4((PPh2)2C2B9H10)2-(PR3)2] (PR3 = PPh3 (2), P(4-MeC6H4)3 (3), P(4-OMeC6H4)3 (4)). The X-ray crystal structure of complex 4 shows a tetrahedral framework of gold atoms, two of which are chelated by the diphosphine, and two are coordinated to one monophosphine ligand each. These compounds are very stable and are obtained in high yield. MP2 calculations suggest that the two types of chemically nonequivalent gold atoms can be formally assigned as Au(I) (those attached to the arsines or phosphines) and Au(0) (those bonded to the anionic diphosphine) and emphasize the role of correlation in the gold-gold interactions. The compounds are luminescent. The emission is assigned to a gold-centered spin-forbidden transition; the assignment of the oxidation state of the gold centers on this basis leads to results coincident with those obtained by theoretical calculations. 相似文献
8.
László Jánosi László Kollár Piero Macchi Angelo Sironi 《Transition Metal Chemistry》2007,32(6):746-752
Pt(diphosphine)X(aryl) complexes [diphosphine = 1,3-bis(diphenylphosphino)propane (dppp), 2,4-bis(diphenylphos phino)pentane (bdpp); aryl = phenyl, 2-thiophenyl; X = Cl, I] have been reacted with ethyl diazoacetate in chloroform.
It has been revealed by in␣situ n.m.r. studies that the starting compounds insert the carbene, formed from ethyl diazoacetate, into the Pt–aryl group resulting
in Pt(diphosphine)X{CH(aryl)COOC2H5}. Depending on the reaction conditions (reaction time, ratio of the reactants) and the ligands various side-reactions have
been observed: (i) the formation of Pt(diphosphine)X2 in chloroform, (ii) the insertion of the :CHCOOC2H5 fragment into the Pt–halide bond of the dihalogeno complexes Pt(diphosphine)X2 resulting in the exclusive formation of Pt(diphosphine)X(CHXCOOC2H5). Diastereoselective insertion reactions have been observed in the presence of (S,S)-bdpp as diphosphine. The Pt{(S,S)-bdpp)}I(Ph) complex has been characterized by X-ray crystallography. 相似文献
9.
《Journal of organometallic chemistry》1987,333(2):253-262
The isomeric butadiene compounds 1,1- and 1,2-[Os3(C4H6)(CO)10] and the acetonitrile compound 1,2-[Os3(CO)10(MeCN)2] react with the diphosphines Ph2P(CH2)nPPh2 (n = 2, 3 or 4) to give separable isomers of [Os3(CO)10(diphosphine)] in which the diphosphine is either bridging or chelating, whereas dppm (n = 1) gives only the 1,2-isomer. The mono-acetonitrile compound [Os3-(CO)11(MeCN)] reacts to give two series of compounds: [Os3(CO)11(diphosphine)], containing one coordinated and one free phosphorus atom, and [Os6(CO)22(diphosphine)] with two Os3(CO)11 groups bridged by the diphosphine. The triphosphine, Ph2PCH2CH2PPhCH2CH2PPh2 (triphos), reacts similarly to give two separable isomers of [Os3(CO)11(triphos)] and two inseparable isomers of [Os6(CO)22(triphos)]. Whereas [Os3(CO)11(dppm)] readily undergoes decarbonylation to give 1,2-[Os3(CO)10(dppm)], other compounds of the type [Os3(CO)11(diphosphine)] are not decarbonylated under the same conditions, but react with Me3NO to give the 1,2-but not the 1,1-isomers of [Os3(CO)10(diphosphine)]. 相似文献
10.
Chen HY Di Tommaso D Hogarth G Catlow CR 《Dalton transactions (Cambridge, England : 2003)》2011,40(2):402-412
New insights into the structural, electronic and catalytic properties of Fe complexes are provided by a density functional theory study of model as well as real [Fe(II)(H)(2)(diphosphine)(diamine)] systems. Calculations conducted using several different functionals on the trans- and cis-isomers of [Fe(II)(H)(2)(S-xylbinap)(S,S-dpen)] complexes show that, as with the [Ru(II)(H)(2)(diphosphine)(diamine)] complexes, the trans-[Fe(II)(H)(2)(diphosphine)(diamine)] complex is the more stable isomer. Analysis of the spin states of the trans-[Fe(II)(H)(2)(diphosphine)(diamine)] complexes also shows that the singlet state is significantly more stable than the triplet and the quintet, as with the [Ru(II)(H)(2)(diphosphine)(diamine)] complexes. Calculations of the catalytic cycle for the hydrogenation of ketones using two model trans-[M(II)(H)(2)(PH(3))(2)(en)] catalysts, where M = Ru and Fe, show that the mechanism of reaction as well as the activation energies are very similar, in particular: (i) the ketone/alcohol hydrogen transfer reaction occurs through the metal-ligand bifunctional mechanism, with energy barriers of 3.4 and 3.2 kcal mol(-1) for the Ru- and Fe-catalysed reactions, respectively; (ii) the heterolytic splitting of H(2) across the M[partial double bond, bottom dashed]N bond for the regeneration of the Ru and Fe catalysts has an activation barrier of 13.8 and 12.8 kcal mol(-1), respectively, and is expected to be the rate determining step for both catalytic systems. The reduction of acetophenone by trans-[M(II)(H)(2)(S-xylbinap)(S,S-dpen)] complexes along two competitive reaction pathways, shows that the intermediates for the Fe catalytic system are similar to those responsible for the high enantioselectivity of (R)-alcohol in those proposed trans-[Ru(II)(H)(2)(S-xylbinap)(S,S-dpen)] catalysed acetophenone hydrogenation reaction. Thus the high enantiomeric excess in the hydrogenation of acetophenone could, in principle, be achieved using Fe catalysts. 相似文献
11.
The complexes [Ni(YR)(triphos)]BPh(4) (Y = S, R = Ph or Et or Y = Se, R = Ph; triphos = (Ph(2)PCH(2)CH(2))(2)PPh) have been prepared and characterized, and the X-ray crystal structure of [Ni(SPh)(triphos)]BPh(4) has been solved. In MeCN, [Ni(YR)(triphos)](+) are protonated by [lutH](+) (lut = 2,6-dimethylpyridine) to give [Ni(YHR)(triphos)](2+). Studies on the kinetics of these equilibrium reactions reveal an unexpected difference in the reactivities of [Ni(SPh)(triphos)](+) and [Ni(SEt)(triphos)](+). In both cases, the reactions exhibit a first-order dependence on the concentration of complex. When R = Ph, the dependence on the concentrations of [lutH(+)] and lut is given by k(obs) = k(1)(Ph)[lutH(+)] + k(-1)(Ph)[lut], which is typical of an equilibrium reaction where k(1)(Ph) and k(-1)(Ph) correspond to the forward and back reactions, respectively. Analogous behavior is observed for [Ni(SePh)(triphos)](+). However, for [Ni(SEt)(triphos)](+), the kinetics are more complicated, and k(obs) = (k(1)k(2)[lutH(+)] + (k(-2) + k(2)))/(k(1)[lutH(+)] + k(-1)[lut]), which is indicative of a mechanism involving two coupled equilibria in which the initial protonation of the thiolate is followed by a unimolecular equilibrium reaction that is assumed to involve the formation of an eta(2)-EtS-H ligand. The difference in reactivity between the complexes with alkyl and aryl thiolate ligands is a consequence of the (Ni(triphos))(2+) site "leveling" the basicities of these ligands. The pK(a)'s of the PhSH and EtSH constituents coordinated to the (Ni(triphos))(2+) are 16.0 and 14.6, respectively, whereas the difference in pK(a)'s of free PhSH and EtSH differ by ca. 4 units. The pK(a) of [Ni(SeHPh)(triphos)](+) is 14.4. The more strongly sigma-donating EtS ligand makes the (Ni(triphos))(2+) core sufficiently electron-rich that the basicities of the sulfur and nickel in [Ni(SEt)(triphos)](+) are very similar; therefore, the proton serves as a bridge between the two sites. The relevance of these observations to the proposed mechanisms of nickel-based hydrogenases is discussed. 相似文献
12.
Triazole-based monophosphines for Suzuki-Miyaura coupling and amination reactions of aryl chlorides 总被引:1,自引:0,他引:1
[reaction: see text] A new class of triazole-based monophosphine 1 (ClickPhos) has been prepared via efficient 1,3-dipolar cycloadditions of readily available azides and acetylenes. Palladium complexes derived from these ligands provide highly active catalysts for Suzuki-Miyaura coupling and amination reactions of aryl chlorides. 相似文献
13.
[structure: see text] Diastereomeric biaryl diphosphine ligands 10 and 11 with added chiral centers on the backbone were synthesized. Substrate-directed asymmetric synthesis occurred in the coupling step of the preparation of the diastereomeric diphosphine oxides. The diastereomeric diphosphine oxides were easily separated by column chromatography with silica gel. Ruthenium catalysts containing these ligands were highly effective in the hydrogenation of 2-(6'-methoxy-2'-naphthyl)propenoic acid and beta-ketoesters. The additional chiral centers had a significant influence on the enantioselectivity and activity of the catalysts. 相似文献
14.
Alkoxy substituted MeO-BIPHEP-type diphosphines ligands for asymmetric hydrogenation of aryl ketones
<正>In this paper,a series of optically active MeO-BIPHEP-type ligands,(S)-6,6′-dimethoxy-2,2'-bis(di-p-alkoxyphenylphosphine)- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects of para-substituted were observed,the results showed that the ruthenium catalysts[diphosphine RuCl_2 diamine]containing both t-Bu and i-Pr substitutions have better activities and enantioselectivities than the non-substituted ruthenium catalysts in the asymmetric hydrogenation of acetophenone. 相似文献
15.
Hems WP McMorn P Riddel S Watson S Hancock FE Hutchings GJ 《Organic & biomolecular chemistry》2005,3(8):1547-1550
Rh diphosphine complexes using DuPhos and JosiPhos as chiral ligands have been immobilised by ion exchange into the mesoporous material MCM-41. When used as catalysts for the enantioselective hydrogenation of dimethyl itaconate and methyl-2-acetamidoacrylate, these heterogeneous catalysts give catalytic performance in terms of yield and enantioselection that are comparable to the corresponding homogeneous catalysts. Furthermore, the heterogeneous catalysts can be readily recovered and reused without loss of catalyst performance. A second immobilisation strategy is described in which [Rh(COD)2]+BF4- is initially immobilised by ion exchange and subsequently modified by the chiral diphosphine and this give comparable catalyst performance. This immobilisation strategy opens up the possibility of easy ligand-screening for parallel synthesis and libraries. 相似文献
16.
The dianionic stannaborate [SnB11H11]2- oxidatively adds iodine at the tin vertex to give the iodinated cluster [I2SnB11H11]2- which maintains a closo structure, albeit having a nido electron count. The iodo-stannaborate [I2SnB11H11]2- is unstable at room temperature, but its structure was elucidated via single-crystal X-ray diffraction at low temperatures. The low-temperature 11B NMR spectrum exhibits a 5:1:5 signal pattern, and the 119Sn NMR shows a resonance at -1039 ppm. Iodination of the zwitterionic stannaborate iron complex Fe(SnB11H11)(triphos) leads to the formation of the corresponding iodo-stannaborate iron complex Fe(I2SnB11H11)(triphos) which features an iodinated stannaborate moiety that has a structure analogous to that of [I2SnB11H11]2-. The zwitterionic iodo-stannaborate complex is stable at room temperature, and the crystal structure and the 1H, 11B, 31P, and 119Sn NMR parameters were determined. 119Sn M?ssbauer spectroscopy supports the assignment of a tin oxidation state of +II for Fe(SnB11H11)(triphos) (delta = 2.71 mm s-1) and +IV for Fe(I2SnB11H11)(triphos) (delta = 1.22 mm s-1). Additional 57Fe M?ssbauer spectra confirm the iron oxidation state +II for both compounds. 相似文献
17.
Pt(diphosphine)X(aryl) complexes [diphosphine = 1,3-bis(diphenylphosphino)propane (dppp); aryl=phenyl, 2-thiophenyl; X=Cl,
I] have been reacted with carbon monoxide in chloroform. It has been revealed by in situ NMR studies that the starting compounds
insert carbon monoxide into the Pt-aryl group resulting in Pt(diphosphine)X{C(O)aryl} complexes. It has been found that the
phenyl complexes are much more reactive than the corresponding 2-thiophenyl complexes. Similarly, higher reactivity has been
observed with iodo than with the chloro complexes. 相似文献
18.
A concise synthesis of a new xylyl-biaryl diphosphine ligand for asymmetric hydrogenation of ketones
Julian P. HenschkeAntonio Zanotti-Gerosa Paul Moran Paul HarrisonBrendan Mullen Guy CasyIan C. Lennon 《Tetrahedron letters》2003,44(23):4379-4383
A concise synthesis of a symmetrical biaryl diphosphine ligand bearing 3,5-dimethylphenyl substituents at phosphorus is described. The ruthenium catalysts [diphosphine RuCl2 diamine] containing the new ligand Xyl-TetraPHEMP were found to be as active and as selective as the state-of-the-art catalysts for homogeneous asymmetric ketone hydrogenation. 相似文献
19.
Fernández D García-Seijo MI Kégl T Petocz G Kollár L García-Fernández ME 《Inorganic chemistry》2002,41(17):4435-4443
The five-coordinate palladium(II) and platinum(II) complexes [M(PP(3))Cl]Cl [M = Pd (1), Pt (2)] (PP(3) = tris[2-(diphenylphosphino)ethyl]phosphine) were prepared by interaction of aqueous solutions of MCl(4)(2-) salts with PP(3) in CHCl(3). Complexes 1 and 2 undergo facile chloro substitution reactions with KCN in 1:1 and 1:2 ratios to afford complexes [M(PP(3))(CN)]Cl [M = Pt (3)] and [M(PP(3))(CN)](CN) [M = Pd (4), Pt (5)] possessing M-C bonds, both in solution and in the solid state. The reaction of 1 and 2 with SnCl(2) in CDCl(3) occurs with insertion of SnCl(2) into M-Cl bonds leading to the formation of [M(PP(3))(SnCl(3))](SnCl(3)) [M = Pd (6), M = Pt (7)]. The isolation as solids of complexes 6 and 7 by addition of SnCl(2) to the precursors requires the presence of PPh(3) which activates the cleavage of M-Cl bonds, favors the SnCl(2) insertion, and does not coordinate to M in any observable extent. Solutions of 6 in CDCl(3) undergo tin dichloride elimination in higher proportion than solutions of 7. The reaction of complexes 1 and 2 with SnPh(2)Cl(2) leads to [M(PP(3))Cl](2)[SnPh(2)Cl(4)] [M = Pd (8)]. Complexes 2, 5, 7, and 8 were shown by X-ray diffraction to contain distorted trigonal bipyramidal monocations [M(PP(3))X](+) [M = Pt, X = Cl(-) (2), X = CN(-) (5), X = SnCl(3)(-) (7); M = Pd, X = Cl(-) (8)], the central P atom of PP(3) being trans to X in axial position and the terminal P donors in the equatorial plane of the bipyramids. The "preformed" catalyst 7 showed a relatively high aldehyde selectivity compared to most of the platinum catalysts. 相似文献
20.
Margraf G Pattacini R Messaoudi A Braunstein P 《Chemical communications (Cambridge, England)》2006,(29):3098-3100
Two tautomers of the new phosphinoaminothiazoline Ph2PNHC=NCH2CH2S, obtained from the reaction of 2-amino-2-thiazoline (ATHZ) with Ph(2)PCl, have been structurally characterized and the intermediate formation of the diphosphine Ph2PN=CN(PPh2)CH2CH2S has been demonstrated experimentally and by DFT calculations; reacts with [AuCl(THT)] to give [(AuCl)2] whereas the bidentate metalloligand cis-[Pt(1(-H))2] reacts with AgOTf to form the Ag-Pt coordination polymer [Ag(infinity)[Pt(1(-H))2](infinity)](OTf)(infinity). 相似文献