- Synthesis and characterization of platinum and palladium clusters with phosphide ligands
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Clusters of composition n, n = 6-10, have been synthesized by reduction of a series of PtII complexes m (G = (OAc)2*PdC3H5, m = 1; G = Cl, OAc, (OAc)2Ag, m = 2) with H2, HCOOH and Na-amalgam.A hydridophosphide PdII complex n was obtained in an analogous manner by reduction of 2 with HCOOH.Additionally a complex with diphenylphosphonic acid as a ligand 2 was obtained and characterized with X-ray data.The formation of O2PPh2 anion under strictly anaerobic reductive conditions implies the transfer of an O atom from the carboxylic ligand to the P atom of the phosphorus-containing ligand.Cleavage of the C-Ph bond seems to be a common process for the reductive reactions of both Pd and Pt phosphine complexes.Phosphide clusters of compositions n and n were characterized with IR, SAXS, EXAFS and NMR data and molecular mass measurements.
- Moiseev, Ilya I.,Kozitsyna, Natalya Yu.,Kochubey, Dmitry I.,Kolomijchuk, Vsevolod N.,Zamaraev, Kirill I.
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- PLATINUM COMPLEX, ITS PREPARATION AND THERAPEUTIC USE
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A platinum complex comprises a chemical structure of Structure I: where L1 and L2 are independently selected from electron donor ligands, including but not limited to halogen ligands, hydroxo ligands, carboxylato ligands, and alkoxido ligands; R1, R2 and R3 are each independently selected from a hydrogen atom, hydrocarbon group, or heterocyclic group; wherein the hydrocarbon group is selected from: alkyl, alkenyl, cycloalkyl, phenyl, and naphthyl which may optionally be substituted by at least one functional group selected from the group consisting of: hydroxy, halogen, alkoxy, alkoxycarbonyl, carboxy, amido, amino, nitro, cyano, carbamate, urea, sulfonyl, sulfenyl, phosphenyl, phosphinyl, sulfide, thioether, thioester, sugar moiety, cyclodextrin, or porphyrin ring; and the heterocyclic group is selected from: pyridyl, piperidyl, azino, azolyl, imidazolyl, triazinyl, furyl or carbozolyl; or two adjacent R1, R2 and R3 groups form a heterocycle or a carbocycle with or without an intermediary hetero atom or intermediary hetero atoms.
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Paragraph 0053; 0057-0059
(2021/12/03)
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- Cis Influence in trans-Pt(PPh3)2 complexes
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The cis influence of a series of anionic ligands X and Y has been evaluated through the magnitude of the Pt-P coupling constants for compounds of formula trans-[PtXY(PPh3)2]. The order of decreasing cis influence was found to be I > Cl > SePh ~ SPh ~ SEt > NO3 > AcO ~ NO2 > H > Me > Ph > mtc (mtc = N,N-dimethylmonothiocarbamato-S); moreover, the cis influences of the various ligands was found to be additive. The X-ray structures of three representative compounds (t-4: X = Cl, Y = NO3; t-5: X = Cl, Y = AcO and t-12: X = Y = NO2) have also been determined. The Royal Society of Chemistry 2009.
- Rigamonti, Luca,Manassero, Carlo,Rusconi, Michele,Manassero, Mario,Pasini, Alessandro
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p. 1206 - 1213
(2009/06/17)
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- The role of anions in addressing the outcome of the reaction of tetramethylthiourea with cis-PtII(phos)2 moieties (phos = PPh3 or 1/2dppe), cyclometallation vs. hydrolysis to monothiocarbamato, and the crystal structure of trans-Bis(N- dimethylmonothiocarbamato)bis(triphenylphosphane)-platinum(II)
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The product of the reaction between tetramethylthiourea (tmtu) and cis-PtII(phos)2 moieties (phos = PPh3, or 1/2 dppe) depends on the anionic species present. With NO3-, CF3CO2-, CF3SO3 -. and BF4-, the cyclometallate cationic complex [Pt(phos)2(tmtu*-C,S)]+ is obtained (tmtu* is tmtu deprotonated at one methyl group). The acetato and malonato complexes are inactive towards such deprotonation, but, in the presence of water, promote tmtu hydrolysis with formation of N-dimethylmonothiocarbamato (mtc) complexes in which mtc is S-coordinated. cis-[Pt(PPh3) 2(mtc)2] isomerises slowly to the trans isomer, whose crystal structure is reported. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Alesi, Maria,Fantasia, Serena,Manassero, Mario,Pasini, Alessandro
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p. 1429 - 1435
(2007/10/03)
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- Reaction of platinum acetate with phosphines and molecular structure of trans-[Pt(OAc)2(PPh3)2]
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An improved synthesis of platinum acetate is reported in detail. This tetrameric complex reacts with PPh3 or P-n-Bu3 at room temperature to give the thermodynamically unstable bis-substituted trans-[Pt(OAc)2L2] complexes, which are not easily accessible via other routes. The structure of the new compound trans-[Pt(OAc)2(PPh3)2] has been determined by X-ray analysis.
- Basato, Marino,Biffis, Andrea,Martinati, Gianluca,Tubaro, Cristina,Venzo, Alfonso,Ganis, Paolo,Benetollo, Franco
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p. 399 - 403
(2008/10/09)
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- Bis(carboxylato) complexes of platinum(II). Structural and bonding analysis of [Pt(O2CR)2(L-L)] [L-L = 2PPh3, Ph2PCH2PPh2 or Fe(C5H4PPh2)2; R = Me, CF3, Pri or Ph]
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Treatment of [PtCl2(L-L)] [L-L = 2 PPh3, Ph2PCH2PPh2(dppm) or Fe(C5H4PPh2)2(dppf)] with Ag(O2CR) (R = Me, CF3, Pri or Ph) at room temperature generally gave [Pt(O2CR)2(L-L)] in moderate to good yields. The crystal and molecular structures of [Pt(O2CMe)2(dppf)]·H2O, [Pt(O2CPh)2(dppf)]·CH2Cl2 and [Pt(O2CCF3)2(dppm)] have been determined by single-crystal X-ray diffractometry. All these complexes show a mononuclear square-planar structure with a chelating diphosphine and two neighbouring (cis) carboxylates in a monodentate mode. These structures contrast those of the parent [Pt4(μ-O2CMe)8] and its derivative [Pt4(en)4(μ-O2CMe)4]4+ (en = ethylenediamine) which are tetrameric, based on octahedral PtII, and contain bridging acetates and direct Pt-Pt bonds. Fenske-Hall molecular orbital calculations of these structures confirmed the existence of Pt-Pt bonding interactions. The presence of hard and electronegative ligands like en and acetate incurs a deficiency in σ-electron density, compared to virtually filled non-bonding orbitals; the former is alleviated by Pt-Pt bonding, d8 Complexes with ligands like phosphines possessing both σ-donating and π-accepting qualities appear to favour the usual square-planar geometry.
- Tan, Agnes L.,Low, Pauline M. N.,Zhou, Zhong-Yuan,Zheng, Weiming,Wu, Bo-Mu,Mak, Thomas C. W.,Hor, T. S. Andy
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p. 2207 - 2214
(2007/10/03)
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- Re(III) COMPLEXES IN THE SYNTHESIS OF PLATINUM ACETATE COMPLEXES AND THE STRUCTURE OF 2
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Reaction of tetrachlorodiacetatodirhenium dihydrate with triphenylphosphineplatinum(II) triacetatoargentate(I) produces a new binuclear platinum complex with acetate bridges, bis2-acetato)acetatotriphenylphosphine>diplatinum(II).The new complex is characterized by x-ray structural analysis, IR, and PMR spectrocopies.The Re(III) complex in this reaction is not only the source of chloride ions, which are necessary for precipitation of silver, and the acetate acceptor, but also the silver(I) reductant which is oxidized during the reaction to Re(IV).
- Kozitsyna, N. Yu.,Surazhskaya, M. D.,Larina, T. B.,Koz'min, P. A.,Kotel'nikova, A. S.,Moiseev, I. I.
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p. 1739 - 1744
(2007/10/02)
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- Insertion of Carbon Dioxide, of CO2-like Molecules, and of Other Unsaturated Compounds into the Platinum-Nitrogen Bond of
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The compound (1) reacts reversibly with carbon dioxide to give (2).Other CO2-like molecules readily and irreversibly insert into the platinum-nitrogen bond of (1); with CS2, PhNCO, and PhNCS the corresponding 1:1 adducts (3), (4), and (5), respectively have been obtained.Compound (2) is an isomer of the insertion product (6), , obtained from the reaction of with PhNCO.A labile insertion product, , (7), was obtained by reaction of (1) with PhCHO, while no reaction was observed between (1) and acetone or diethyl carbonate.However, compound (1) reacts with EtO2C-N=N-CO2Et to give the substitution product (8), .The reactions of compound (2) towards mineral acids, organic acids, benzoyl chloride, and sulphonyl chlorides have been studied.The products are identical to those obtained from the corresponding reactions of (1).I.r., 1H, 31P, and 195Pt n.m.r. spectra of the new compounds are reported and discussed.
- Cenini, Sergio,Porta, Francesca,Pizzotti, Maddalena,Crotti, Corrado
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p. 163 - 168
(2007/10/02)
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- Dinuclear, metal-metal-bonded platinum(III) compounds. 2. Synthesis and properties of complexes containing the [Pt2(HPO4)4(B)2]2- anions (B = a heterocyclic tertiary amine) or the [Pt2(H2PO4)(HPO4) 3(py)2]- ion
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The reactions of phosphoric acid solutions containing the diplatinum(III) anion [Pt2(HPO4)4]2- with heterocyclic tertiary amines afford yellow complexes of stoichiometry (BH)2[Pt2(HPO4)4(B)2], where B = pyridine, 4-methylpyridine, or 3,4-dimethylpyridine. These products are probably contaminated with small amounts of the mixed salts (BH)[Pt2(H2P-O4)(HPO4) 3(B)2]·H2O, a complex of this type apparently being the principal product when 4-phenylpyridine is used as the nitrogen base. During attempts to grow suitable crystals of the pyridine (py)-containing complex (pyH)2[Pt2(HPO4)4(py)2], we instead isolated (pyH)[Pt2(H2PO4)(HPO4) 3(py)2]·H2O, the identity of which was determined by an X-ray structure analysis. The crystals are orthorhombic, and the structure was solved and refined in space group Pc21n (a nonstandard setting of Pna21). The unit cell dimensions are as follows: a = 8.460 (2) A?; b = 16.476 (6) A?; c = 19.466 (6) A?; V = 2713 (2) A?3; Z = 4. The structure was refined to R = 0.031 and Rw = 0.039. The Pt-Pt distance is 2.494 (1) A?, the mean Pt-O(coord) distance is 2.004 [4] A?, and the mean P-O(coord) distance is 1.528 [4] A?. The Pt-N distances are 2.11 (2) and 2.18 (1) A?, with the py planes being almost perpendicular to each other and staggered with respect to the Pt-O bonds. The water molecule is loosely hydrogen bonded to the [Pt2(H2PO4)(HPO4) 3(py)2] ion. The pattern of P-O distances, the occurrence of hydrogen-bonded O?O contacts, and the chemical analysis are all consistent with the formulation of this compound. Preliminary studies of the reaction of (pyH)2[Pt2(HPO4)4(py)2] with triphenylphosphine and tert-butyl isocyanide have been carried out. Mononuclear products such as Pt(PPh3)2(O2CCH3)2 (formed in glacial acetic acid) and Pt(CN-t-Bu)2(CN)2 attest to the relative ease with which reductive cleavage of the Pt-Pt bond occurs.
- Conder, Harold L.,Cotton, F. Albert,Falvello, Larry R.,Han, Scott,Walton, Richard A.
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p. 1887 - 1891
(2008/10/08)
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