12266-72-7Relevant academic research and scientific papers
Coordination chemistry of the 2-pyridyidiphosphine ligands, (py)2P(CH(CH2)3CH)P(py)2 and (py)2P(CH2)2P(py)2 (py = 2-pyridyl), with platinum(II) and ruthenium(II). Ruthenium-catalyzed hydrogenation of imines
Jones, Nathan D.,MacFarlane, Kenneth S.,Smith, Martin B.,Schutte, Richard P.,Rettig, Steven J.,James, Brian R.
, p. 3956 - 3966 (1999)
The synthesis and characterization of a range of Pt(II) and Ru(II) complexes containing the new 2-pyridyldi-phosphine ligand, d(py)pcp = (py)2P(CH(CH2)3CH)P(py)2 (made as a racemate) and the previously reported d(py)pe = (py)2P(CH2)2P(py)2 are given (py = 2-pyridyl). The Pt complexes made were cis-PtX2(d(py)pcp) (X = Cl (1), I (2)), cis-PtX2(d(py)pe) (X = Cl (3), I (4)), [Pt(d(Py)pcp)2][PF6]2 (5), and [Pt(d(py)pe)2][PF6]2 (6); these all contain P,P-bonded diphosphine ligand, as evidenced by 31P NMR data and by crystallographic data in the case of 2 and 3. The X-ray structure of d(py)pe is also reported. The complexes RuX2(P,P,N-d(py)pcp)(PPh3) have cis-halogens and a P,P,N-bonding mode of the pyridyldiphosphine (which incorporates a four-membered P,N-chelate ring) with either a mer-arrangement (in 7a, X = Cl) or a fac-arrangement of the three P donor atoms (in 7b (X = Cl), 8 (X = Br), 9 (X = I)); cis-RuCl2(dppb)(P,N-PPh2(py)) (12) (dppb = Ph2P(CH2)4PPh2) is included because it has a donor set corresponding to that in 7b. Use of the purely P,P donor Ph2P(CH(CH2)3-CH)PPh2 (dppcp), made as a racemate, affords trans-RuCl2(dppcp)2 (10) and tran?-RuCl2(dppcp)(dppb) (11). Crystallographic data for 7a, 7b, and 12 are reported together with the NMR data for all the Ru complexes. Preliminary results show that the Ru complexes 7b, 8, and 9 are effective precursors for catalytic H2-hydrogenation of aldimines.
Alkyl Transfer in the Heterodinuclear Organometallic Complex. Preparation of Organo(1,5-cyclooctadiene)platinum-tricarbonyl(cyclopentadienyl)tungsten
Komiya, Sanshiro,Endo, Isao
, p. 1709 - 1712 (1988)
Methyl(1,5-cyclooctadiene)platinum-tricarbonyl(cyclopentadienyl)tungsten has been prepared by the reaction of methylchloro(1,5-cyclooctadiene)platinum(II) with sodium tricarbonyl(cyclopentadienyl)tungstate(0).Methyl transfer from platinum to tungsten smoo
Platinum Cyclooctadiene Complexes with Activity against Gram-positive Bacteria
Frei, Angelo,Ramu, Soumya,Lowe, Gabrielle J.,Dinh, Hue,Semenec, Lucie,Elliott, Alysha G.,Zuegg, Johannes,Deckers, Anke,Jung, Nicole,Br?se, Stefan,Cain, Amy K.,Blaskovich, Mark A. T.
supporting information, p. 3165 - 3171 (2021/07/16)
Antimicrobial resistance is a looming health crisis, and it is becoming increasingly clear that organic chemistry alone is not sufficient to continue to provide the world with novel and effective antibiotics. Recently there has been an increased number of reports describing promising antimicrobial properties of metal-containing compounds. Platinum complexes are well known in the field of inorganic medicinal chemistry for their tremendous success as anticancer agents. Here we report on the promising antibacterial properties of platinum cyclooctadiene (COD) complexes. Amongst the 15 compounds studied, the simplest compounds Pt(COD)X2 (X=Cl, I, Pt1 and Pt2) showed excellent activity against a panel of Gram-positive bacteria including vancomycin and methicillin resistant Staphylococcus aureus. Additionally, the lead compounds show no toxicity against mammalian cells or haemolytic properties at the highest tested concentrations, indicating that the observed activity is specific against bacteria. Finally, these compounds showed no toxicity against Galleria mellonella at the highest measured concentrations. However, preliminary efficacy studies in the same animal model found no decrease in bacterial load upon treatment with Pt1 and Pt2. Serum exchange studies suggest that these compounds exhibit high serum binding which reduces their bioavailability in vivo, mandating alternative administration routes such as e. g. topical application.
Photochemistry of 1,5-Cyclooctadiene Platinum Complexes for Photoassisted Chemical Vapor Deposition
Liu, Hanwen,Brewer, Christopher R.,Walker, Amy V.,McElwee-White, Lisa
, p. 4565 - 4574 (2020/12/23)
Quantum yields for disappearance of (COD)PtMe2 (1a) and (COD)PtMeCl (1b) were determined at 334 nm in C6D6 solvent. Chain reactions initiated by formation of a methyl radical were proposed to be the cause of quantum yields higher than unity (φ = 5.52 ± 0.40 for 1a) when the reaction mixtures included C4F9I. The chain reactions were suppressed in the presence of the radical trap 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), which resulted in measured disappearance quantum yields of φ = 0.037 ± 0.003 for (COD)PtMe2 and φ = 0.44 ± 0.02 for (COD)PtMeCl at 334 nm. Weak luminescence was observed for 1a and 1b, and it was determined that emissive decay is not competitive with Pt-CH3 bond homolysis. DFT studies enabled assignment of both SBLCT and MLCT transitions in the UV/vis spectra of 1a, while 1b only exhibits MLCT transitions. These effects can be attributed to the symmetry of the molecule and its electronic structure.
Cytotoxicity and NMR studies of platinum complexes with cyclooctadiene ligands
Enders, Mirja,Goerling, Benjamin,Braun, Alexander B.,Seltenreich, Judith E.,Reichenbach, Linus F.,Rissanen, Kari,Nieger, Martin,Luy, Burkhard,Schepers, Ute,Braese, Stefan
supporting information, p. 4027 - 4034 (2014/10/15)
The synthesis of a series of platinum complexes containing cyclooctadiene ligands with the general structure PtMeL(R-cod) (where L = Cl, I, nC 3F7, iC3F7, nC8F 17, Me, aryl, alkynyl and R = H, Me, Et, iPr, nBu, iBu, nHex, Ph) is presented. All complexes are remarkably stable and were obtained in excellent yields. Their structure in both solution and the solid state were explored by crystal structures and multinuclear (1H, 13C, 19F, 195Pt) NMR spectroscopy. Cytotoxicity experiments with selected complexes in HeLa cells revealed higher toxicity in comparison to that of cisplatin for most of the structures.
Cooperation between cis and trans influences in cis-Pt II(PPh3)2 complexes: Structural, spectroscopic, and computational studies
Rigamonti, Luca,Forni, Alessandra,Manassero, Mario,Manassero, Carlo,Pasini, Alessandro
, p. 123 - 135 (2010/03/04)
The relevance of cis and trans influences of some anionic ligands X and Y in cis-[PtX2(PPh3)2] and cis-[PtXY(PPh 3)2] complexes have been studied by the X-ray crystal structures of several derivatives (X2 = (AcO)2 (3), (NO3)2 (5), Br2 (7), I2 (11); and XY = Cl(AcO) (2), Cl(NO3) (4), and Cl(NO2) (13)), density functional theory (DFT) calculations, and one bond Pt-P coupling constants, JPtp. The latter have allowed an evaluation of the relative magnitude of both influences. It is concluded that such influences act in a cooperative way and that the cis influence is not irrelevant when rationalizing the 1 JPtp values, as well as the experimental Pt-P bond distances. On the contrary, in the optimized geometries, evaluated through B3LYP/def2-SVP calculations, the cis influence was not observed, except for compounds CIPh (21), Ph2 (22), and, to a lesser extent, Cl(NO2) (13) and (NO2) 2(14). A natural bond order analysis on the optimized structures, however, has shown how the cis influence can be related to the s-character of the Pt hybrid orbital involved in the Pt-P bonds and the net atomic charge on Pt. We have also found that in the X-ray structures of cis-[PtX 2(PPh3)2] complexes the two Pt-X and the two Pt-P bond lengths are different each other and are related to the conformation of the phosphine groups, rather than to the crystal packing, since this feature is observed also in the optimized geometries.
Reaction of the carbodiphosphorane Ph3P=C=PPh3 with platinum(II) and -(0) compounds: Platinum induced activation of C-H bonds
Petz, Wolfgang,Kutschera, Christian,Neumueller, Bernhard
, p. 5038 - 5043 (2008/10/09)
The complex [(cod)PtI2] (cod = 1,5-cyclooctadiene) reacts with 3 equiv of the hexaphenyl-carbodiphosphorane Ph3P=C=PPh3 (1) in THF solution to give the novel Pt(II) complex [(η3-C 8H11)Pt(C6H4PPh2CPPh 3)] (2) along with the salt [HC(PPh3)2]I. In addition to the coordination of the ylidic carbon atom at the Pt atom, 2 contains two further Pt-C σ bonds originating from H to Pt exchange in the ortho position of one phenyl group of the carbodiphosphorane ligand and in the former cod ligand. The resulting C8H11 moiety is coordinated to the Pt atom in an η3 manner via a double bond and a σ bond and contains a further uncoordinated double bond. From a 1:1 reaction mixture in toluene/CH2Cl2 the majority of the crystals consist of the salt [HC(PPh3)2]I·2CH 2Cl2 (3) with small amounts of platinum compounds as byproducts. The Pt(0) complex [(PPh3)2Pt(CH 2=CH2)] does not react with 1 but decomposes at elevated temperatures to give the known dinuclear complex [Pt2-(PPh 3)2(μ-PPh2] (4). The complexes 2 and 4 and the salt 3 could be characterized by X-ray analyses and the usual spectroscopic methods.
High-pressure methods as a tool in organometallic syntheses: Facilitation of oxidative addition to platinum(II)
Skauge, Andrew R.L.,Shalders, Richard D.,Swaddle, Thomas W.
, p. 1998 - 2001 (2007/10/03)
High-pressure (2 GPa) batch reactors now commercially available may offer substantial accelerations of organometallic syntheses, without resort to heating, when the activation process is multicentered or involves the generation and solvation of ions. As an example of the latter class of reactions, the kinetics of the oxidative additions of methyl and ethyl iodides (RI) to dimethyl(2,2′-bipyridine)platinum(II) in acetone have been studied over the pressure range 0-200 MPa. The volumes of activation ΔV1?, if assumed to be constant over this range, are -11.7 ± 0.3 and -9.7 ± 0.7 cm3 mol-1, respectively, implying an acceleration of ca. 3000-fold for a batch synthesis of this son at 2 GPa. However, a possible slight pressure dependence of ΔV1? may reduce this acceleration to ca. 1 000-fold. The ΔV1? data and the 500-fold retardation on going from R = Me to R = Et are consistent with an SN2 attack of PtII on the α-carbon in the alkyl iodides, forming I- and [RMe2Pt(bpy)]+.
Preparation and properties of inclusion compounds of transition-metal complexes of cycloocta-1,5-diene and norbornadiene with cyclodextrins
Harada, Akira,Yamamoto, Shyoko,Takahashi, Shigetoshi
, p. 2560 - 2563 (2008/10/08)
Inclusion compounds of rhodium and platinum complexes of cycloocta-1,5-diene (COD) and norbornadiene (NBD) with cyclodextrins were prepared. Two-to-one (cyclodextrin to guest) inclusion compounds were obtained in high yields in a crystalline state by the treatment of β-cyclodextrin (β-CD) with bis(μ-halo)bis(η4-cycloocta-1,5-diene)dirhodium, [Rh(μ-X)(COD)]2 (X = Cl, Br, I), and bis(μ-chloro)bis(η4-norbornadiene)dirhodium, [Rh(μ-Cl)(NBD)]2. The formation of inclusion compounds is selective. One-to-one inclusion compounds were obtained by the reaction of β-CD with (cycloocta-1,5-diene)platinum dihalides, Pt(COD)X2 (X = Cl, Br, I), in high yields, while γ-CD formed 1:1 inclusion compounds with Pt(COD)I2 but not with Pt(COD)Cl2. α-Cyclodextrin did not form inclusion compounds with any transition-metal complexes of cyclooctadiene and norbornadiene. The inclusion compounds are thermally stable and do not liberate the guest when heated to 200°C in vacuo at which temperature the nonincluded guest [Rh(μ-Cl)(COD)]2 already decomposed. The inclusion compounds were characterized by 1H NMR, IR, UV, and circular dichroism spectra. A large induced Cotton effect was observed with β-CD-[Rh(μ-Cl)(COD)]2. The 1H NMR spectrum of [Rh(μ-Cl)(COD)]2 in the presence of β-CD shows two sets of resonances for two different CD species that are assigned to free β-CD and the complexed β-CD, respectively. The binding mode will be discussed.
Tetranuclear homo- or heterobimetallic asymmetric palladium(II)-platinum(II) complexes with single halide bridges. Molecular structure of [Pt(C6F5)2(μ-Br)Pd(η 4-1,5-C8H12)(μ-Br)Pt(C6F 5)2(μ-Br)Pd-(η4-1,5-C8H 12)(μ-Br)]
Usón,Forniés,Tomás,Menjón,Welch
, p. 1318 - 1323 (2008/10/08)
Treatment of cis-[M(C6X5)2(THF)2] (M = Pd, Pt; X = F, Cl; THF = tetrahydrofuran) with M′X′2(COD) (M′ = Pd, Pt; X′ = Cl, Br, I; COD = 1,5-cyclooctadiene) results in the formation of homo- and heteronuclear palladium or platinum complexes of general formula [(C6X5)2M(μ-X′) 2M′(COD)]n which are binuclear (n = 1) in CHCl3 solutions. The molecular structure of [Pt(C6F5)2(μ-Br)Pd(COD)(μ-Br)Pt(C 6F5)2(μ-Br)-Pd(COD)(μ-Br)] has been established by single-crystal X-ray crystallography, showing that the complex is tetranuclear in the solid state. The molecule resides on a center of symmetry and can be regarded as an eight-membered ring skeleton being made up of two Pt(C6F5)2 and two Pd(η4-1,5-C8H12) groups in an alternate way connected by single bromide bridges. Crystal data: monoclinic, a = 26.742 (6) A?, b = 9.3916 (18) A?, c = 18.133 (5) A?; β = 108.424 (22)°; space group C2/c; Z = 4. The structure has been solved from diffractometer data by direct and Fourier methods and refined by full-matrix least squares to R = 0.0369 for 3059 observed reflections.
