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1.
Arylmercury compounds of the type Ar2Hg and ArHgX (X = Cl, OAc) have been synthesized and characterized by 1H and 13C NMR spectroscopy; the Ar group was either 2-Me2NCH2C6H4 or (S)-2-Me2NCH(Me)C6H4, both of which contain N-donor ligands. The observation of anisochronous NMe resonances in (S)-2-Me2NCH(Me)C6H4HgX (X = Cl, OAc) at low temperature indicates that in solution the mercury centre is three-coordinate as a result of stable intramolecular HgN coordination  相似文献   

2.
Complexes [{2,6-(Me2NCH2)2C6H3} (p-tolylNYNR)PtHgBrCl] (Y  CH, N; R  Me, Et, i-Pr) have been prepared by the reaction of [{2,6-(Me2NCH2)2C6H3}-PtBr] with [Hg(p-tolylNYNR)Cl]. Similar complexes were obtained, although in lower yields, from exchange reactions of [{2,6-(Me2NCH2)2C6H3} (RCO2)-PtHg(O2CR)Br] with p-tolylNNN(H)-p-tolyl and p-tolylNC(H)N(H)Et.The proposed structure for these heterodinuclear compounds involves a Pt-to-Hg donor bond which is bridged by a triazenido (Y  N) or a formamidino (Y  CH) group, the five-membered ring thus formed acting as a stabilizing factor. The absence of a subsequent electron transfer reaction is ascribed to the constraints of the terdentate 2,6-(Me2NCH2)2C6H3 ligand, which fixes the N-donor atoms in mutual trans-positions.The use of p-tolylNYNR, where R is an alkyl group, results in the formation of two isomers of [{2,6-(Me2NCH2)2C6H3} (p-tolylNYNR)PtHgBrCl] with p-tolyl-N and alkyl-N sites bonded either to Pt or Hg. The relative abundance of these isomers varies systematically with the nature of the group R. It is suggested that the ratio is determined during the formation of the complexes and that both steric and electronic factors are important.  相似文献   

3.
Platinum(II) and palladium(II) complexes containing chelating acyl ligands have been synthesized from salicylaldehyde, 2-hydroxynaphthaldehyde and 2-hydroxy-3-methoxybenzaldehyde. The platinum(II) complexes [Pt(acyl)L2], acyl  OC6H4CO, OC10H6CO, O(m-CH3OC6H3CO), L  tertiary phosphine, 1/2 diphenylphosphinoethane, can be isolated with both monodentate and chelating diphosphines, whereas for palladium only the compounds with chelating phosphines are readily obtainable. The reactions of [Pt(OC6H4CO)L2] with HCl afford trans-[PtCl(OHC6H4CO)L2], L  monodentate tertiary phosphine and cis-[PtCl(OHC6H4CO)L2], L2  1,2-bis-diphenylphosphinoethane, in which the metal—carbon bond remains intact. The structure of [Pt(OC6H4CO)-(P(p-CH3C6H4)3)2] has been determined by X-ray diffraction methods and found to have the expected square planar structure. Some relevant bond lengths and angles are: PtP; 2.271(4) and 2.348(5) Å; PtC; 1.96(2) Å and PtO; 2.07(1) Å; PPtP  101°, CPtO  82°.  相似文献   

4.
[2-(Me2NCH2)C6H4]HgCl (1) was prepared by reacting HgCl2 with [2-(Me2NCH2)C6H4]Li in diethyl ether. The reactions of 1 with the sodium or ammonium salt of the appropriate thiophosphinato ligand, in 1:1 molar ratio, afford the isolation of [2-(Me2NCH2)C6H4]Hg[S(S)PR2] [R=Me (2), Et (3), Ph (4)], [2-(Me2NCH2)C6H4]Hg[S(O)PPh2] (5) and [2-(Me2NCH2)C6H4]Hg[S(S)P(OiPr)2] (6). The compounds were investigated by IR and multinuclear NMR (1H, 13C and 31P) spectroscopy. The molecular structures of 1 and 4 were determined by single-crystal X-ray diffraction. Due to the strong intramolecular coordination of the N atom of the pendant CH2NMe2 arm [Hg(1)-N(1) 2.764(6) and 2.725(4) Å in 1 and 4, respectively] both compounds exhibit a T-shaped (C,N)HgX core in the molecular unit, with almost linear arrangement of the covalent bonds [C(1)-Hg(1)-Cl(1) 176.93(18)° in 1, and C(1)-Hg(1)-S(1) 169.54(16)° in 4]. The crystals of 1 contain discrete monomeric molecules, while the crystals of 4 contain dimer associations built through asymmetric bridging dithiophosphinato ligands [Hg(1)-S(1) 2.3911(16) Å, Hg(1)?S(2a) 3.102(2) Å], thus resulting in an overall pseudo-trigonal bipyramidal (or seesaw) (C,N)HgS2 core, with the nitrogen atom and the weekly bonded sulfur atom in equatorial positions [N(1)-Hg(1)?S(2a) 82.01(10)°].  相似文献   

5.
A series of homodinuclear Pt compounds containing the anionic, potentially terdentate NCN ligand (NCN=[C6H3(Me2NCH2)2-2,6]) or its 4-ethynyl derivative were prepared. The two platinum centres are linked together in two different fashions: (i) directly linked by an ethynyl or diethynylphenyl group (head-to-head) and (ii) indirectly bonded by a ethynyl- or butadiynyl-linked bis-NCN ligand (tail-to-tail). The reaction of the head-to-head σ,σ′-ethynylide complex {Pt}CC{Pt} ({Pt}=[Pt(C6H3{CH2NMe2}2-2,6)]+) with [CuCl]n yields {Pt}Cl and [Cu2C2]n, while with [Cu(NCMe)4][BF4] a Cu(I) bridged complex was formed: [(η2-{Pt}CC{Pt})2Cu][BF4]. The results of cyclic voltammetry experiments reveal that both connection modes of the two platinum centres lead to electrochemically independent Pt–NCN units. The X-ray crystal structure analysis of the neutral, tail-to-tail bridging butadiyne bis-NCNH ligand [C6H3(CH2NMe2)-1,3-(CC)-5]2 is reported.  相似文献   

6.
The complexes cis-[M(Ph2PC6H4-2-S)2] M=Ni, Pd, Pt were stereoselectively synthesized by transmetallation reactions of [M(Cl)2(NCC6H5)2] M=Pd, Pt or NiCl2·6H2O with [Sn(R)2(Ph2PC6H4-2-S)2] R=Ph, nBu or tBu. The conformation of the Pd and Pt derivatives being unequivocally confirmed by single crystal X-ray diffraction studies showing both metal centers to be into a slightly distorted square planar environment, the main distortion being due to the steric hindrance caused by the aromatic rings in the phosphine moiety.  相似文献   

7.
A number of halogen complexes of Pd, Pt and Rh with 1,5-hexadiene have been synthesized;three of them, C6H10PdBr2, C6H10PtBr2 and (C6H10RhCl)2, for the first time. An intermediate while preparing C6H10PdCl2 was the polynuclear polymeric moiety [C6H10(PdCl2)4]n· IR, Raman and ESCA spectroscopy show that the diallylic ligand in all the complexes has the cis-configuration and that the strength of the metaldiallyl bond increases in the series Pd < Pt < Rh.  相似文献   

8.
Diorganodiselenide [2-(Et2NCH2)C6H4]2Se2 (1) was obtained by hydrolysis/oxidation of the corresponding [2-(Et2NCH2)C6H4]SeLi derivative. The treatment of [2-(Et2NCH2)C6H4]2Se2 with elemental sodium in THF resulted in [2-(Et2NCH2)C6H4]SeNa (2). Reactions between alkali metal selenolates [2-(R2NCH2)C6H4]SeM′ (R = Me, Et; M′ = Li, Na) and MCl2 (M = Zn, Cd) in a 2:1 molar ratio resulted in the [2-(R2NCH2)C6H4Se]2M species [R = Me, M = Zn (3), Cd (4); R = Et, M = Zn (5), Cd (6)]. The new compounds were characterized by multinuclear NMR (1H, 13C, 77Se, 113Cd) and mass spectrometry. The crystal and molecular structures of 1, 3 and 4 revealed monomeric species stabilized by N → Se (for 1) and N → M (for 3 and 4) intramolecular interactions.  相似文献   

9.
The synthesis and structural characterization by 1H NMR and 197Au Mössbauer spectroscopy as well as by chiral labelling of the built-in ligands of three different types of arylgold(I) compounds is described.197Au Mössbauer data revealed that the benzyl- and arylgold(I) triphenylphosphine complexes which bear potential coordinating substituents at an ortho position still contain linearly coordinated AuI with 2c-2e gold(I)carbon bonds. The observation of isochronous NME resonances in (S)-2-Me2NCH(Me)C6H4AuPPh3 confirms that no additional intramolecular AuN coordination occurs in solution. Preliminary results of an X-ray diffraction study of 2,6-(MeO)2C6H3AuPPh3 are reported (R = 0.040, PAuC1 angle 172.6°. Unsymmetrical AuC1C2 and AuC1C6 angles of 126.4 and 117.4°, respectively).Pure, uncomplexed arylgold(I) compounds have been isolated from the reaction of diarylgoldlithium compounds (arylaurates) with trimethyltin bromide. (S)-2-Me2NCHMeC6H4Au has a dimeric structure which most likely consists of two monomeric units associated by intermolecular AuN coordination thus forming a ten-membered chelate ring. The structure of insoluble 2-Me2NCH2C6H4Au and 2-Me2NC6H4Au are less clear. The former compound probably has a structure similar to (S)-2-Me2NCHMeC6H4Au (IS/QS values for two-coordinate AuI centers). However, the strongly deviating IS and QS values of 2-Me2NC6H4Au indicate that a polynuclear structure for this compound similar to that proposed for 2-Me2NC6H4Cu cannot be excluded (a polymeric structure containing 2-Me2NC6H4 groups which span three Au atoms by 3c-2e Au2C bonds and AuN coordination).The mixed Au/Cu cluster (2-Me2NCH2C6H4)4Au2Cu2 is accessible via the 12 reaction of (2-Me2NCH2C6H4)4Au2Li2 with CuI. Molecular weight and 1H NMR studies point to a tetranuclear structure in solution, while mass spectrometry shows fragment ions with m/e corresponding to (2-Me2NCH2C6H4)3Au2Cu2+, (2-Me2NCH2C6H4)3Cu2Au+, (2-Me2NCH2C6H4)2CuAu2+ and of (2-Me2NCH2C6H4)2Au+.  相似文献   

10.
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 PN 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   

11.
The selective, single-step synthesis of (2-Me2NCHZC6H4)RSnX2, in which Z  H or Me, R  Me or Ph and X  Cl or Br, starting from the tetranuclear copper cluster compound (2-Me2NCHZC6H4)4Cu4 and RSnX3 is described. Reaction of (2-Me2NCH2C6H4)4Cu4 with SnBr4 in a 1/2 molar ratio afforded (2-Me2NCH2C6H4)2SnBr2 in almost quantitative yield.1H NMR spectroscopic data of these novel compounds, which are monomeric in solution, indicate that: (i) intramolecular SnN coordination renders the Sn atom in (2-Me2NCHZC6H4)RSnX2 pentacoordinate, with the organo ligands residing in the equatorial plane of a trigonal bipyramidal structure, and the Sn atom in (2-Me2NCH2C6H4)2SnBr2 hexacoordinate, with trans organo groups and a cis arrangement for the Br and the N atoms; (ii) in pyridine the Sn atom in (2-Me2NCHZC6H4)RSnX2 becomes hexacoordinate by complex formation with the solvent but that intramolecular SnN coordination has been retained.The stereochemical lability of the pentacoordinate Sn center in the diorganotin dihalides (2-Me2NCHZC6H4)RSnX2, which contain a dissymmetrical equatorial plane, has been established on the basis of the dynamic NMR spectra of  相似文献   

12.
[Pd(C6F5)2(CNR)2] (R = Cy, But, p-MeC6H4 (p-Tol)) react with [PdCl2(NCPh)2] to give [Pd2(μ-Cl)2(C6F5)2(CNR)2]. In refluxing benzene insertion of isocyanide into the C6F5Pd bonds occurs only for R = p-Tol, to give a imidoyl bridged polynuclear complex cis-[Pd2 (μ-Cl)2[μ-C(C6F5) = N(Tol-p)]2n]. This complex reacts with (a) Tl(acac) to give [Pd2{μ-C(C6F5) = N(Tol-p)}2(acac)2]; (b) neutral monodentate ligands to afford dimeric complexes [Pd2{μ-C(C6F5) = N(Tol-p)}2Cl2L2] (L = NMe3, py, 4-Me-py, SC4H8), and (c) isocyanides to give insoluble complexes of the same composition which are thought to be polymeric, [Pd(CNR)Cl{μ-C(C6F5) = N(p-Tol)}]n (R = p-Tol, Me, But). Thermal decomposition of cis-[Pd2 (μ-Cl)2 [μ-C(C6F5) = N( p-Tol)]2n] gives the diazabutadiene species (p-Tol)NC(C6F5)C(C6F5)N(p-Tol) in high yield.  相似文献   

13.
The cleavage of the Se-Se bond in [2-(Me2NCH2)C6H4]2Se2 (1) was achieved by treatment with SO2Cl2 (1:1 molar ratio) or elemental halogens to yield [2-(Me2NCH2)C6H4]SeX [X = Cl (2), Br (3), I (4)]. Oxidation of 1 with SO2Cl2 (1:3 molar ratio) gave [2-(Me2NCH2)C6H4]SeCl3 (5). [2-(Me2NCH2)C6H4]SeS(S)CNR2 [R = Me (6), Et (7)] were prepared by reacting [2-(Me2NCH2)C6H4]SeBr with Na[S2CNR2] · nH2O (R = Me, n = 2; R = Et, n = 3). The reaction of 3 with K[(SPMe2)(SPPh2)N] resulted in isolation of [2-(Me2NCH2)C6H4]Se-S-PMe2N-PPh2S (8). The compounds were characterized by solution NMR spectroscopy (1H, 13C, 31P, 77Se, 2D experiments). The solid-state molecular structures of 2, 4-8 were established by single crystal X-ray diffraction. All compounds are monomeric, with the N atom of the pendant CH2NMe2 arm involved in a three-center-four-electron N?Se-X (X = halogen, S) bond. This results in a T-shaped coordination geometry for the Se(II) atom in 2, 4, 6-8. In 5, the Se(IV) atom achieves a square pyramidal coordination in the mononuclear unit. Loosely connected dimers are formed through intermolecular Se?Cl interactions (3.40 Å); the overall coordination geometry being distorted octahedral. In all compounds hydrogen bonds involving halide or sulfur atoms generate supramolecular associations in crystals.  相似文献   

14.
The complex dicarbonylbis(diphenylethylphosphine)platinum, Pt(CO)2[P(C6H5)2(C2H5)]2, crystallizes in either of the enantiomorphous space groups P3121 (No. 152) and P3221 (No. 154) with cell dimensions a = 10.64(1), c = 22.06(1) Å, U = 2163 Å3; pc = 1.564 g/cm3 for Z = 3, pm = 1.55(3) g/cm3. The intensities of 1177 independent reflections have been determined by counter methods with MoKα monochromatized radiation. The structure has been solved by the heavy atom method. The refinement, carried out by full-matrix least squares down to a final R factor of 0.042, has enabled the absolute configuration of the crystal sample (space group P3121) to be ascertained. The molecule is roughly tetrahedral, and has the metal atom lying on a two-fold axis of the cell. Bond parameters are: PtC = 1.92(2) Å, PtP = 2.360(4) Å, CPtC = 117(1)° and PPtP = 97.9(2)°. The PtC2 and PtP2 moieties make a dihedral angle of 86.0(3)°. The overall C2 symmetry of the molecule is probably only a statistically averaged situation, a disorder in the PtCO interactions being apparent from the orientations of the thermal ellipsoids of the C and O atoms.  相似文献   

15.
Bis(cycloocta-1,5-diene)platinum reacts with 2,3,4,5-tetraphenylfulvene to afford the complex [Pt(η2-CH2C5Ph4)(cod)] (cod  C8H12) in which the metal atom is coordinated to the exo-cyclic double bond of the fulvene. Related compounds [Pt(η2-CH2C5Ph4L2] (L  PPh3, PMePh2, PMe2Ph, AsPh3 or CNBut have also been prepared and characterised. Reaction of the complexes [Pt(C2H4)2(L)] (L  P(cyclo-C6H11)3, PPh3 or AsPh3) with 2,3,4,5-tetraphenylfulvene yields the compounds [Pt(C2H4)(η2-CH2C5PH4)(L)]. NMR data for the new species are reported and discussed. 6,6-Diphenylfulvene reacts with [Pt(cod)2] and PPh3 (12 mol ratio) to give the complex [Pt(η2-C5H4CPh2)-(PPh3)2] in which the metal atom is bonded to carbon atoms C(2) and C(3) of the fulvene ring. This was established by an X-ray diffraction study. Crystals are monoclinic, space group P21/n, with Z  4 in a unit cell of dimensions a  13.761(4), b  21.653(13), c  17.395(6) Å, β,  104.46(2)°. The structure has been solved and refined to R  0.064 (R′  0.064) for 3139 independent diffracted intensifies measured at room temperature. The platinum atom is in a trigonal environment formed by the two ligated phosphorus atoms and the CC bond of the fulvene which is elongated to 1.52(3) Å. The c5 fulvene ring is planar, and makes an angle of 108° with the coordination plane around the platinum. In this plane the metal atom is slightly asymmetrically bonded with PtC 2.15(2) and 2.24(2) Å, and PtP 2.280(6) and 2.301(6) Å.  相似文献   

16.
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] (XCl, 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 PtP(1) 2.332(7), PtP(2) 2.341(8), PtC 2.08(2), and PtI 2.666(2) Å, and angles (a) C(1)PtI, P(1), P(2): 176.9(8), 91.6(6), 93.4(6), (b) IPtP(1), P(2): 87.1(2), 88.5(2), and (c) P(1)P(2), 166.8(3), and (d) PtC(1)P(3), 118(1)°.  相似文献   

17.
Nitrile-functionalized NCN-pincer complexes of type [MBr(NC-4-C6H2(CH2NMe2)2-2,6)] (6a, M = Pd; 6b, M = Pt) (NCN = [C6H2(CH2NMe2)2-2,6]) are accessible by the reaction of Br-1-NC-4-C6H2(CH2NMe2)2-2,6 (2b) with [Pd2(dba)3 · CHCl3] (5a) (dba = dibenzylidene acetone) and [Pt(tol-4)2(SEt2)]2 (5b) (tol = tolyl), respectively. Complex 6b could successfully be converted to the linear coordination polymer {[Pt(NC-4-C6H2(CH2NMe2)2-2,6)](ClO4)}n (8) upon its reaction with the organometallic heterobimetallic π-tweezer compound {[Ti](μ-σ,π-CCSiMe3)2}AgOClO3 (7) ([Ti] = (η5-C5H4SiMe3)2Ti).The structures of 6a (M = Pd) and 6b (M = Pt) in the solid state are reported. In both complexes the d8-configurated transition metal ions palladium(II) and platinum(II) possess a somewhat distorted square-planar coordination sphere. Coordination number 4 at the group-10 metal atoms M is reached by the coordination of two ortho-substituents Me2NCH2, the NCN ipso-carbon atom and the bromide ligand. The NC group is para-positioned with respect to M.  相似文献   

18.
The compounds trans-[Pt(OCHO)R(PPh3)2] (R = C6Cl5; 2,3,4,6-C6HCl4; 2,3,4,5-C6HCl4; 2,5-C6H3Cl2) have been prepared by treatment of [PtIR(PPh3)2] with AgClO4 followed by reaction with NaOCHO in methanol. The cis isomers have been obtained by the direct reaction of HCO2H with compounds containing PtHg bonds. For these and the analogous compounds containing C6F5 ligands, the dependence of J(31P195Pt) on R has been studied, and the effects of cis-R shown to be in the opposite direction from those of trans-R ligands.  相似文献   

19.
The reaction of [Pt2(μ-S)2(P-P)2] (P-P=2PPh3, 2PMe2Ph, dppf) [dppf=1,1-bis(diphenylphosphino)ferrocene] with cis-[M(C6F5)2(PhCN)2] (M=Ni, Pd) or cis-[Pt(C6F5)2(THF)2] (THF=tetrahydrofuran) afforded sulfide aggregates of the type [{Pt23-S)2(P-P)2}M(C6F5)2] (M=Ni, Pd, Pt). X-ray crystal analysis revealed that [{Pt23-S)2(dppf)2}Pd(C6F5)2], [{Pt23-S)2(PPh3)2}Ni(C6F5)2], [{Pt23-S)2(PPh3)2}Pd(C6F5)2] and [{Pt23-S)2(PMe2Ph)2}Pt(C6F5)2] have triangular M3S2 core structures capped on both sides by μ3-sulfido ligands. The structural features of these polymetallic complexes are described. Some of them display short metal-metal contacts.  相似文献   

20.
Infrared spectra of creatinine (H3CNC(NH)NHCOCH2) (creat), cis-Pt(creat)2(NO2)2 and Pt(creat)4(CIO4)2 have been recorded in the range 50–4000 cm−1. The fundamental vibrations for the creatinine molecule were assigned by normal coordinate analysis in the generalized valence force field approximation. The spectrum of cis-Pt(creat)2(NO2)2 was interpreted by comparison with the creatinine vibrational modes. Additionally the Pt(creat)4(ClO4)2 infrared spectrum has been involved to help the assignment.  相似文献   

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