A novel unsymmetrically disubstituted propanedithiolate compound [Fe2(CO)4(κ2-dmpe)(μ-pdt)] (1) (pdt = SCH2CH2CH2S, dmpe = Me2PCH2CH2PMe2) was synthesized by treatment of [Fe2(CO)6(μ-pdt)] with dmpe in refluxing THF. Compound 1 was characterized by single-crystal X-ray diffraction analysis. Protonation of 1 with HBF4·Et2O in CH2Cl2 gave at room temperature the μ-hydrido derivative [Fe2(CO)4(κ2-dmpe)(μ-pdt)(μ-H)](BF4)] (2). At low temperature, 1H and 31P–{1H} NMR monitoring revealed the formation of a terminal hydride intermediate 3. Comparison of these results with those of a VT NMR study of the protonation of symmetrical compounds [Fe2(CO)4L2(μ-pdt)] [L = PMe3, P(OMe)3] suggests that in disubstituted bimetallic complexes [Fe2(CO)4L2(μ-pdt)], dissymmetry of the complex is required to observe terminal hydride species. Attempts to extend the series of chelate compounds [Fe2(CO)4(κ2-L2)(μ-pdt)] by using arphos (arphos = Ph2AsCH2CH2PPh2) were unsuccessful. Only mono- and disubstituted derivatives [Fe2(CO)6−n(Ph2AsCH2CH2PPh2)n(μ-pdt)] (n = 1, 4a; n = 2, 4b), featuring dangling arphos, were isolated under the same reaction conditions of formation of 1. Compound 4b was structurally characterized. 相似文献
The ligand (i-Pr)2PCH2(oxazoline) (1a), of the P,N-donor type, was reacted with [PdMeCl(COD)] to yield the square planar methylpalladium(II) complex [PdClMe(P,N)] (P,N = 1a) (2a), from which the complex [PdMe(P,N)OTf] (OTf = OSO2CF3) (3a) was obtained by AgOTf-promoted chloride abstraction. The alkyl complexes (P,N = 1a) (5a, R = H; 7a, R = C(O)OMe) have been isolated from the initial CO/ethylene or CO/methyl acrylate insertion steps into the Pd–Me bond of 3a, respectively, and spectroscopically characterized. Complexes 2a, 3a and 7a have been fully characterized by single crystal X-ray diffraction. Complex 7a is still a rare example of a structurally characterized CO/methyl acrylate stepwise insertion product. These complexes are relevant to the alternating copolymerization of olefins and carbon monoxide catalyzed by palladium complexes. In addition, the centrosymmetric dinuclear complex trans-[Pd(μ-Cl){(i-Pr)2PCH2(oxazoline)}]2(OTf)2 (6) has been obtained and characterized by X-ray diffraction; it appears to be the first dinuclear complex of the type [Pd(μ-Cl)(P,N)]2 to be characterized by X-ray crystallography.
Résumé
Le ligand (i-Pr)2PCH2(oxazoline) (1a), de type donneur P,N, réagit avec [PdClMe(COD)] pour former le complexe plan carré méthylpalladium(II) [PdClMe(P,N)] (P,N = 1a) (2a), à partir duquel le complexe [PdMe(P,N)OTf] (OTf = OSO2CF3) (3a) a été obtenu par abstraction de chlorure à l'aide de AgOTf. Les complexes alkyles (P,N = 1a) (5a, R = H; 7a, R = C(O)OMe), ont été isolés lors des premières étapes d'insertion de CO/éthylène ou de CO/acrylate de méthyle, respectivement, dans la liaison Pd–Me de 3a, et caractérisés par méthodes spectroscopiques. Les complexes 2a, 3a et 7a ont été complètement caractérisés par diffraction des rayons X sur monocristal. Le complexe 7a est un exemple encore rare de produit d'insertion par étapes de CO/acrylate de méthyle qui ait été caractérisé structuralement. Ces complexes sont pertinents pour la copolymérisation alternée d'oléfines et de monoxyde de carbone catalysée par les complexes du palladium. En outre, le complexe dinucléaire centrosymétrique trans-[Pd(μ-Cl){(i-Pr)2PCH2(oxazoline)}]2(OTf)2 (6) a été obtenu et caractérisé par diffraction des rayons X; il s'agit du premier complexe dinucléaire de type [Pd(μ-Cl)(P,N)]2 à être caractérisé par diffraction des rayons X. 相似文献
The new zinc(II) coordination polymer catena-poly[{aqua(η2-indole-3-carboxylato-O,O′)zinc}-μ-indole-3-carboxylato-O:O′], [Zn(I3CA)2(H2O)]n [Zn(I3CA)2(H2O)]n has been synthesized and characterized using infrared and Raman spectroscopy and X-ray single-crystal diffraction analysis. The crystals are monoclinic, space group Cc, with a = 33.319(7), b = 5.985(1), c = 8.291(2) Å, V = 1653.1(6) Å3 and z = 4. Each zinc centre is five-coordinated by the bidentate chelating indole-3-carboxylato, one oxygen atom bridging indole-3-carboxylato, water molecule and one oxygen atom bridging indole-3-carboxylato from an adjacent [Zn(I3CA)2(H2O)] unit. The Zn–O distances of 1.978(4), 1.987(3), 1.977(4), 1.983(3) and 2.519(4) Å, are typical for distances of such complexes. The infrared and Raman spectroscopic data of [Zn(I3CA)2(H2O)]n in the solid state are supported by X-ray analysis. The theoretical wavenumbers, infrared intensities and Raman scattering activities have been calculated by the density functional methods (B3LYP and mPW1PW) with the D95V**/LanL2DZ and 6-311++G(d,p)/LanL2DZ basis sets. The theoretical wavenumbers, infrared intensities and Raman scattering activities show a good agreement with experimental. Detailed band assignment has been made on the basis of the calculated potential energy distribution (PED). The results provide information on the strength of zinc-ligand bonding in complex. 相似文献
The treatment of [PdL3(NH3)]OTf (L3 = (PEt3)2(Ph) (1), (2,6-(Cy2PCH2)2C6H3) (3)) with NaNH2 in THF afforded dimeric and monomeric parent-amido palladium(II) complexes with bridging and terminal NH2, respectively, anti-[Pd(PEt3)(Ph)(μ-NH2)]2 (2) and Pd(2,6-(Cy2PCH2)2C6H3)(NH2) (4). The dimeric complex 2 crystallizes in the space group P21/n with a = 13.228(2) Å, b = 18.132(2) Å, c = 24.745(2) Å, β = 101.41(1)°, and Z = 4. It has been found that there are two crystallographically independent molecules with Pd(1)–Pd(2) and Pd(3)–Pd(4) distances of 2.9594 (10) and 2.9401(9) Å, respectively. The monomeric amido complex 4 protonates from trace amounts of water to give the cationic ammine species [Pd(2,6-(Cy2PCH2)2C6H3)(NH3)]+. Complex 4 reacts with diphenyliodonium triflate ([Ph2I]OTf) to give aniline complex [Pd(2,6-(Cy2PCH2)2C6H3)(NH2Ph)]OTf (5). Reaction of 4 with dialkyl acetylenedicarboxylate (DMAD, DEAD) yields diastereospecific palladium(II) vinyl derivative (Z)–(Pd(Cy2PCH2)2C6H3)(CR = CR(NH2)) (R = CO2Me (6a), CO2Et (6b)). Reacting complexes 6a and 6b with p-nitrophenol produces (Pd(Cy2PCH2)2C6H3)(OC6H4–p-NO2) (8) and cis-CHR = CR(NH2), exclusively. 相似文献
The catena-poly[{aqua(η2-indole-3-propionato-O,O′)zinc}-η2-:-μ-indole-3-propionato-O,O′:-O], [Zn(I3PA)2(H2O)]n was prepared and characterized by infrared spectroscopy and X-ray structure determination. The crystals are monoclinic, space group Pc, with a = 21.380(2), b = 5.9076(7), c = 8.1215(9) Å, V = 1020.2(2) Å3 and Z = 2. The central zinc atom shows the coordination distorted from ideal octahedral. Each zinc centre is coordinated by two oxygen atoms of the bidentate chelating indole-3-propionato (I3PA), two oxygen atoms tridentate chelating-bridging I3PA, water molecule and one oxygen atom tridentate chelating-bridging I3PA from an adjacent [Zn(I3PA)2(H2O)] unit. The infrared spectrum of [Zn(I3PA)2(H2O)]n in the solid state is supported by X-ray analysis. The theoretical wavenumbers and infrared intensities have been calculated by the density functional methods (B3LYP and mPW1PW) with the 6-311++G(d,p)/LanL2DZ basis sets. The theoretical wavenumbers, infrared intensities show a good agreement with experimental data. Detailed band assignment has been made on the basis of the calculated potential energy distribution (PED). 相似文献
Palladium–biscarbene complexes derived from N,N′-bis(1,2,4-triazol-1-yl)methane, which bear an alkyl chain functionalized with a hydroxyl group, have been synthesized ([Pd(L1)Br2] (6) and [Pd(L1)I2] (7) [L1 = 1,1′-(3-hydroxypropylidene)bis(4-butyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene)]). Each product is obtained as a non-equimolecular mixture of two conformers. The hydroxyl group has been replaced by bromide and methanesulphonate and ( [Pd(L2)Br2] [L2 = 1,1′-(3-bromopropylidene)bis(4-butyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene)] (9)) and ([Pd(L3)Br2] [L3 = 1,1′-(3-methanesulphonyloxypropylidene)-bis(4-butyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene)] (10)) were obtained, respectively, as mixtures of conformers. All compounds consist of a six-membered metallacyclic structure in a boat conformation. Major conformers present the functionalized chain in the axial position, while in minor conformers it is located in the equatorial position. 相似文献
Computational methods are used to investigate catalytic hydrophenylation of ethylene using complexes of the type [(Y)M(L)(CH3)(NCMe)]n+ [Y = Mp, n = 1; Y = Tp, n = 0; M = Ru or Os; L = PMe3, PF3, or CO; Mp = tris(pyrazolyl)methane; Tp = hydrido-tris(pyrazolyl)borate]. The conversion of ethylene and benzene to ethylbenzene with [(Y)M(L)(Ph)]n+ as catalyst involves four steps: (1) ethylene coordination, (2) ethylene insertion into the M–Ph bond, (3) benzene coordination, and (4) benzene C–H activation. DFT calculations form the basis to compare stoichiometric benzene C–H activation by [(Y)M(L)(CH3)(NCMe)]n+ complexes to yield methane and [(Y)M(L)(Ph)(NCMe)]n+. In addition, starting from the 16-electron species [(Y)M(L)(Ph)]n+, potential energy surfaces for the formation of ethylbenzene are calculated to reveal the impact of modifications to the scorpionate ligand (Mp or Tp), co-ligand (L) and metal center (M). 相似文献
The mixed ligand complex [La(hfa)3(Phen)2] (I) was obtained by the interaction of La(hfa)3 and Phen; its composition does not depend on the stoichiometry of the reagents. According to the X-ray single crystal analysis data, complex I crystallizes in the monoclinic space group P21/n, with a = 13.583(3) Å, b = 16.959(3) Å, c = 18.860(4) Å, β = 94.71(3)° and Z = 4. The structure of I consists of isolated mononuclear molecules, the coordination number of La being 10. Thermal behaviour and composition of the vapor phase have been studied for I by thermal analysis and mass-spectrometry using a Knudsen cell. The mixed ligand complex I was found to sublime congruently in the temperature range 370–460 K: [La(hfa)3(Phen)2](s) = [La(hfa)3(Phen)](g) + Phen(g), ΔrH0(T) = 316.2 ± 1.8 kJ/mol. 相似文献
To obtain reliable thermodynamic data for Na2S(s), solid-state EMF measurements of the cell Pd(s)|O2(g)|Na2S(s), Na2SO4(s)|YSZ| Fe(s), FeO(s)|O2(g)ref| Pd(s) were carried out in the temperature range 870 < T/K < 1000 with yttria stabilized zirconia as the solid electrolyte. The measured EMF values were fitted according to the equation Efit/V (±0.00047) = 0.63650 − 0.00584732(T/K) + 0.00073190(T/K) ln (T/K). From the experimental results and the available literature data on Na2SO4(s), the equilibrium constant of formation for Na2S(s) was determined to be lg Kf(Na2S(s)) (±0.05) = 216.28 − 4750(T/K)−1 − 28.28878 ln (T/K). Gibbs energy of formation for Na2S(s) was obtained as ΔfG∘(Na2S(s))/(kJ · mol−1) (±1.0) = 90.9 − 4.1407(T/K) + 0.5415849(T/K) ln (T/K). By applying third law analysis of the experimental data, the standard enthalpy of formation of Na2S(s) was evaluated to be ΔfH∘(Na2S(s), 298.15 K)/(kJ · mol−1) (±1.0) = −369.0. Using the literature data for Cp and the calculated ΔfH∘, the standard entropy was evaluated to S∘(Na2S(s), 298.15 K)/(J · mol−1 · K−1) (±2.0) = 97.0. 相似文献
Five new hydrogen-bonded solvated iron(II) complexes of pyrazolyl- and imidazolyl-based N,N-chelating ligands have been synthesised. Water to ligand-NH hydrogen-bonded bridges occur in the pseudo-dimeric complexes {cis-[Fe(pypzH)2(NCX)2]2(μ-OH2)(H2O)2} · H2O · MeOH (where X = S or Se), and in the chain complex {cis-[Fe(pypzH)2(NCS)2](μ-OH2)}n. A “half” spin-crossover (Tc = 125 K) was observed in the dimeric X = Se complex by means of magnetic measurements and no thermal hysteresis occurred between 4 and 300 K. The crystal structure at 123 K showed Fe–N distances consistent with the magnetism. Each Fe in the dimeric unit was structurally equivalent in the HS–LS state. Removal of the solvate molecules led to HS–HS behaviour over the temperature range 4–300 K. The pseudo-dimer with X = S also showed HS–HS behaviour as did the monomeric analogue cis-[Fe(pypzH)2(NCS)2]H2O and a structurally different methanol-bridged dimer {cis-[Fe(pyimH)2(NCS)2]2(μ-MeOH)2} · 2MeOH (pypzH = 2-(1H-pyrazol-3-yl)-pyridine; pyimH = 2-(1H-imidazol-2-yl)-pyridine). 相似文献
Cationic palladium(II) and rhodium(I) complexes bearing 1,2-diaryl-3,4-bis[(2,4,6-tri-t-butylphenyl)phosphinidene]cyclobutene ligands (DPCB–Y) were prepared and their structures and catalytic activity were examined (aryl = phenyl (DPCB), 4-methoxyphenyl (DPCB–OMe), 4-(trifluoromethyl)phenyl (DPCB–CF3)). The palladium complexes [Pd(MeCN)2(DPCB–Y)]X2 (X = OTf, BF4, BAr4 (Ar = 3,5-bis(trifluoromethyl)phenyl)) were prepared by the reactions of DPCB–Y with [Pd(MeCN)4]X2, which were generated from Pd(OAc)2 and HX in MeCN. On the other hand, the rhodium complexes [Rh(MeCN)2(DPCB–Y)]OTf were prepared by the treatment of [Rh(μ-Cl)(cyclooctene)2]2 with DPCB–Y in CH2Cl2, followed by treatment with AgOTf in the presence of MeCN. The cationic complexes catalyzed conjugate addition of benzyl carbamate to α,β-unsaturated ketones. 相似文献
The hydrogen reaction in concentrated HCl(aq) solutions is a key reaction for the CuCl(aq)/HCl(aq) electrolytic cell. Here, electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) were used to obtain new data for the hydrogen reaction on platinum submerged in highly concentrated acidic solutions at 25 °C and 0.1 MPa. LSV and EIS data were collected for Pt in 0.5 mol/L H2SO4(aq), 1 mol/L HCl(aq) and 7.71 mol/L HCl(aq) solutions. It was found that exchange current density (j0) values varied between 1 and 2 mA/cm2. An equivalent circuit model was used to obtain comparable j0 and limiting current density values from EIS data relative to values obtained with LSV data. It was found that as the concentration of acid increased, a noticeable decrease in the performance was observed. 相似文献
Equilibrium between low-spin [CoIII(SQ)(Cat)(N–N)] and high-spin [CoII(SQ)2(N–N)] redox isomers, where SQ is semiquinonate (charge: −1, spin: 1/2), Cat is catecholate (charge: −2, spin: 0) and N–N is chelating nitrogen donor ligand, respectively, is a representative valence tautomeric phenomenon. To elucidate independently the spin state of the cobalt ion and that of benzoquinone-derived ligands in the solid state, we measured 13C MAS NMR spectrum of 3,5-di-t-butyl-1,2-benzoquinone and 2H MAS NMR spectrum of deuterated 2,2′-bipyridine for [Co(3,5-di-t-butyl-1,2-benzoquinone)2(2,2′-bipyridine)] · x(C6H5CH3) and its deuterated analogue in a temperature range of 200–350 K. Irreversible change of an effective magnetic moment μeff of a virgin sample was observed around 370 K due to a partial loss of crystal solvent and a change of crystal structure, whereas the sample annealed at 390 K showed a crystal structure different from the reported one and a reversible change of μeff, which is ascribed to equilibrium between Co(III)-form (S = 1/2) and Co(II)-form (S = 3/2). Based on the shifts and the number of NMR peaks for the annealed sample, we concluded that (1) interconversion between redox isomers occurs faster than NMR time scale (>104 s−1) in the solid state, (2) intraconversion between SQ and Cat in Co(III)-form also occurs much faster than 5 × 104 s−1 even at 198 K and (3) electron spins on SQ ligands in Co(II)-form are quenched probably due to a strong antiferromagnetic coupling between the two SQ ligands. The enthalpy and the entropy of the interconversion were estimated to be 17 kJ/mol and 54 J/(K mol), respectively. For the virgin metastable phase, SQ and Cat were clearly distinguished by 13C MAS NMR spectrum. The solid-state high-resolution NMR spectrum is useful to detect independently the change of spin states of benzoquinone-derived radical and metal ion. 相似文献
We report on the synthesis and crystal structures of two new zinc coordination polymers with 4,4′-oxybis(benzoate) (oba) ligands. Single crystals of [Zn2(oba)2(azpy)(dmf)2] · 6DMF(azpy = 4,4′-azopyridine) and [Zn2(oba)2(bpe)] · 2DMF · 4H2O (bpe = trans-1,2-bis(4-pyridyl)ethylene) were prepared by treatment of Zn(CH3COO)2 · 2H2O with the H2oba and bis-pyridine type ligands, azpy and bpe, respectively, in DMF. Compound [Zn2(oba)2(azpy)(dmf)2] · 6DMF has a unique ladder structure comprising of heteroorganic bridges, in which the Zn–oba chains construct the side rails, while the Zn–azpy–Zn parts construct the rungs of the ladder framework. Despite the large size of the cavities, these ladder chains stack without interpenetration, and the cavities in the ladder framework are partially connected to create one-dimensional channel-like cavities. Compound [Zn2(oba)2(bpe)] · 2DMF · 4H2O exhibits a three-dimensional coordination framework that is comprised of heteroorganic bridges. The framework is interwoven by two-dimensional layers of [Zn2(oba)2] and the Zn2–bpe chains. The three-dimensional framework, which contains large cavities, about 13 × 11 Å2 in area, has a high porosity and a density of only 0.53 g cm−3. 相似文献
A new indium hydroxyphosphate containing silver, AgIn[PO3(OH)]2, has been synthesized using hydrothermal method. It crystallizes in the P21/c space group with the cell parameters a = 6.6400(2) Å, b = 14.6269(6) Å, c = 6.6616(4) Å, β = 95.681(5)°, V = 643.82(6) Å3, Z = 4. Its three-dimensional framework, built up of corner-sharing PO3(OH) tetrahedra and InO6 octahedra, presents intersecting tunnels running along <111> and [100] directions, in which the Ag+ cations are located. The presence of hydroxyl groups has been confirmed from IR spectroscopy studies and hydrogen atoms were located from the single crystal X-ray diffraction study. The structural relationships with the other compounds of general formula AIMIII[PO3(OH)]2 are analyzed. 相似文献
A systematic investigation of the reactions of Cu(ClO4)2 · 6H2O with maleamic acid (H2L) in the presence of 2,2′-bipyridine (bpy) has been carried out. The chemical and structural identity of the products depends on the solvent, the absence or presence of external hydroxides in the reaction mixture and the molar ratio of the reactants. Various reaction schemes have led to the isolation of the complexes [Cu2(HL)2(bpy)2(H2O)2](ClO4)2 (1), [Cu2(HL)2(bpy)2(H2O)2](ClO4)2 · 2H2O (1 · 2H2O), [Cu(L′′)(bpy)]n · 2nH2O (2 · 2nH2O), [Cu2(L′′)(bpy)2(H2O)2]n(ClO4)2n · 0.5nH2O (3 · 0.5nH2O), [Cu2(L′′)2(bpy)2] · 2MeOH (5 · 2MeOH), [Cu2(L′)2(bpy)2(ClO4)2] (6) and [Cu(ClO4)2(bpy)(MeCN)2] (7b), where L′′2? and L′? are the maleate(?2) and monomethyl maleate(?1) ligands, respectively. The HL? ion has been transformed to L′′2? and L′? in the known compounds 2 · 2nH2O and 6, respectively, via metal ion-assisted processes involving hydrolysis (2 · 2nH2O) and methanolysis (6) of the primary amide group. The reaction that leads to 6 takes place through the formation of the mononuclear complex [Cu(ClO4)2(bpy)(MeOH)2] (7a), whose structure was assigned on the basis of its spectral similarity with the structurally characterized complex 7b. The structures of the cations in 1 and 1 · 2H2O consists of two CuII atoms bridged by the carboxylate groups of the two HL? ligands, each exhibiting the less common η2 coordination mode; a chelating bpy molecule and a H2O ligand complete square pyramidal coordination at each metal centre. The structure of the dinuclear repeating unit in the 1D coordination polymer 3 · 0.5nH2O consists of two CuII atoms bridged by two syn,synη1:η1:μ2 carboxylate groups belonging to two L′′2? ions; each ligand bridged two neighboring [CuII,II2] units thus promoting the formation of a helical chain. The structure of the dinuclear molecule of complex 5 · 2MeOH consists of two CuII atoms bridged by two η2 carboxylate groups from two L′′2? ligands; the second carboxylate group of each maleate(?2) ligand is monodentately coordinated to CuII, creating a remarkable seven-membered chelating ring. The L′? ion behaves as a carboxylate-type ligand in 6, with the carboxylate group being in the familiar syn,synη1:η1:μ2 coordination mode; a chelating bpy molecule and a coordinated ClO4? complete five-coordination at each CuII centre. The crystal structures of the complexes are stabilized by various H-bonding patterns. Characteristic IR bands of the complexes are discussed in terms of the known structures and the coordination modes of the ligands. 相似文献
The crystalline one-dimensional compounds, [M2(bza)4(pyz)]n (bza = benzoate; pyz = pyrazine; M = CuII (1)) and [M2(bza)4(2-mpyz)]n (2-mpyz = 2-methylpyrazine; M = RhII (2), CuII (3)), demonstrate gas absorbency of NO. The amounts of adsorbed NO gas are 0.61 for 1, 0.30 for 2, and 0.23 for 3 per M2 unit at 195 K (800 Torr). The crystals of 1 adsorbed more NO molecules than did those of 2 and 3. The magnetic susceptibilities of the NO-inclusion crystals indicate that included NO molecules interact antiferromagnetically with neighboring guests without dimerization to N2O2. Magnetic behaviors indicated NO aggregation in the narrow 1D channels of 1–3 under unsaturated adsorption conditions. 相似文献
The reactions of [MCl2(P∩P)] and [MCl2(PR3)2)] with 1-mercapto-2-phenyl-o-carborane/NaSeCboPh and 1,2-dimercapto-o-carborane yield mononuclear complexes of composition, [M(SCboPh)2(P∩P)], [M(SeCboPh)2(P∩P)] (M = Pd or Pt; P∩P = dppm (bis(diphenylphosphino)methane), dppe (1,2-bis(diphenylphosphino)ethane) or dppp (1,3-bis(diphenylphosphino)propane)) and [M(SCboS)(PR3)2] (2PR3 = dppm, dppe, 2PEt3, 2PMe2Ph, 2PMePh2 or 2PPh3). These complexes have been characterized by elemental analysis and NMR (1H, 31P, 77Se and 195Pt) spectroscopy. The 1J(Pt–P) values and 195Pt NMR chemical shifts are influenced by the nature of phosphine as well as thiolate ligand. Molecular structures of [Pt(SCboPh)2(dppm)], [Pt(SeCboPh)2(dppm)], [Pt(SCboS)(PMe2Ph)2] and [Pt(SCboS)(PMePh2)2] have been established by single crystal X-ray structural analyses. The platinum atom in all these complexes acquires a distorted square planar configuration defined by two cis-bound phosphine ligands and two chalcogenolate groups. The carborane rings are mutually anti in [Pt(SCboPh)2(dppm)] and [Pt(SeCboPh)2(dppm)]. 相似文献
The reactions of [MCl2(P∩P)] and [MCl2(PR3)2)] with 1-mercapto-2-phenyl-o-carborane/NaSeCboPh and 1,2-dimercapto-o-carborane yield mononuclear complexes of composition, [M(SCboPh)2(P∩P)], [M(SeCboPh)2(P∩P)] (M = Pd or Pt; P∩P = dppm (bis(diphenylphosphino)methane), dppe (1,2-bis(diphenylphosphino)ethane) or dppp (1,3-bis(diphenylphosphino)propane)) and [M(SCboS)(PR3)2] (2PR3 = dppm, dppe, 2PEt3, 2PMe2Ph, 2PMePh2 or 2PPh3). These complexes have been characterized by elemental analysis and NMR (1H, 31P, 77Se and 195Pt) spectroscopy. The 1J(Pt–P) values and 195Pt NMR chemical shifts are influenced by the nature of phosphine as well as thiolate ligand. Molecular structures of [Pt(SCboPh)2(dppm)], [Pt(SeCboPh)2(dppm)], [Pt(SCboS)(PMe2Ph)2] and [Pt(SCboS)(PMePh2)2] have been established by single crystal X-ray structural analyses. The platinum atom in all these complexes acquires a distorted square planar configuration defined by two cis-bound phosphine ligands and two chalcogenolate groups. The carborane rings are mutually anti in [Pt(SCboPh)2(dppm)] and [Pt(SeCboPh)2(dppm)]. 相似文献
Reaction of [RhCl(cod)]2 with 2,7-bis(diphenylphosphino)-1,8-naphthyridine (dpnapy) and 2,6-xylyl isocyanide (XylNC) in the presence of NH4PF6 afforded the dirhodium(I) complex, [Rh2(μ-dpnapy)2(XylNC)4](PF6)2 (5), and similar procedures using [MCl2(cod)] (M = Pt, Pd) resulted in the formation of [Pt2(μ-dpnapy)2(XylNC)4](PF6)4 (6) and [Pd2Cl2(μ-dpnapy)2(XylNC)2](PF6)2 (7). Complexes 5–7 were characterized by elemental analysis, IR, UV–Vis, 1H and 31P{1H} NMR, and ESI mass spectroscopic techniques, to involve a small and rigid d8 {M2(μ-dpnapy)2} metallomacrocycle. Complex 5 readily incorporated a silver(I) ion into the macrocycle to afford [Rh2Ag(μ-dpnapy)2(XylNC)4](PF6)3 (8) which was characterized by X-ray crystallography. The Ag(I) ion is trapped by two trans N atoms of dpnapy ligands, resulting in an asymmetric Rh–Ag⋯Rh structure, determined as a disordered model in the crystal structure, and however, in a CH2Cl2 solution, a dynamic interconversion of the two Ag-trapped sites was observed with low-temperature NMR studies, which was further supported by DFT molecular orbital calculations. When an acetonitrile solution of complex 5 was treated over a droplet of mercury(0), the polymeric compound formulated as {[Rh(μ-dpnapy)(XylNC)2](PF6)}n (9) was isolated as yellow single crystals, which were revealed by X-ray crystallography to consist of C6 helical rods along c axis with a pitch of 33.5 Å (rise of unit = 5.6 Å) and a diameter of 20.64 Å. 相似文献
