Synthesis of dimethylplatinum(IV) compounds, [{PtMe2X2}n], [{PtMe2XY}n], and, in solution, fac-[PtMe2X(H2O)3]+, where X and Y are anionic ligands

1996 ◽  
Vol 74 (11) ◽  
pp. 2008-2017 ◽  
Author(s):  
Trevor G. Appleton ◽  
Campbell J. D'Alton ◽  
John R. Hall ◽  
Michael T. Mathieson ◽  
Mark A. Williams
Keyword(s):  
Key Words ◽  
Oxidative Addition ◽  
Analogous Reaction ◽  
Anionic Ligands ◽  
Concentrated Solution ◽  
Aqueous Hclo ◽  
Methyl Pyridine

Oxidative addition of X2 (X = Cl, Br, I) to cis-[PtMe2L2] (L = pyridine, py, or L2 = N,N,N′,N′-tetramethylethylenediamine (tmen) gave [PtMe2X2L2]. For X = Br, I, treatment with aqueous HClO4 gave insoluble [{PtMe2X2}n], but for X = Cl, [PtMe2Cl2(H2O)2] remained in solution, with [{PtMe2Cl2}n] depositing only from concentrated solution. [PtMe2L2] (L = py, 1/2(tmen)) with water gave [PtMe2(OH)2L2], which, on treatment with HClO4 gave cis-[PtMe2(H2O)4](ClO4)2 in solution. Water also reacted with [PtMe2(nbd)] (nbd = norbornadiene) to give [{PtMe2](OH)2}n]•mH2O. Alcohols ROH (R = Me, Et) with cis-[PtMe2py2] gave [PtMe2(OR)(OH)py2], which reacted with aqueous HClO4 solution to give fac-[PtMe2(OR)(H2O)3]ClO4 in solution. Addition of chloride to this solution caused precipitation of [{PtMe2(OR)Cl}n]. Reaction of [{PtMe2XY}n] with AgNO3 in water gave fac-[PtMe2X(H2O)3](NO3) in solution (X = Y = Cl, Br, I or Y = Cl, X = OR); for X = I added acid was necessary to prevent precipitation of [{PtMe2I(OH)}n]. Reaction of a solution of fac-[PtMe2Br(H2O)3](NO3) with AgNO2 gave fac-[PtMe2(NO2)(H2O)3](NO3) in solution, but an analogous reaction with AgSCN gave a complex in solution formulated as fac-[PtMe2(SCN)(H2O)3](NO3) only in low yield. Key words: platinum, methyl, pyridine, aqua, alkoxide, oxidative addition, NMR.

Oxidative addition chemistry of dimethyl(dipyridyl ketone)platinum(II)

2005 ◽  
Vol 83 (6-7) ◽  
pp. 595-605 ◽  
Author(s):  
Fenbao Zhang ◽  
Michael E Broczkowski ◽  
Michael C Jennings ◽  
Richard J Puddephatt
Keyword(s):  
Hydrogen Peroxide ◽  
Key Words ◽  
Acetyl Chloride ◽  
Oxidative Addition ◽  
Protonated Form ◽  
Supramolecular Polymer ◽  
Hydrolysis Of ◽  
Mecn Solution ◽  
Dipyridyl Ketone ◽  
Methyl Triflate

The dimethylplatinum(II) complex [PtMe2(DPK)] (DPK = di-2-pyridyl ketone) undergoes easy oxidative addition to give platinum(IV) complexes. For example, reaction of [PtMe2(DPK)] with MeI gave [PtIMe3(DPK)], reaction with N-chlorosuccinimide in methanol gave [PtCl(OMe)Me2(DPK)], and reaction with [FN(CH2CH2)2NCH2Cl][BF4]2 in MeCN gave [PtF(NCMe)Me2(DPK)][BF4]. In several cases, the ketone group of the DPK ligand took part in the reactions. For example, oxidation of [PtMe2(DPK)] by air or hydrogen peroxide gave [Pt(OH)Me2(DPKOH)] (DPKOH = κ3-NN′O-(2-C5H4N)2C(OH)O), which reacted with HCl to give [PtClMe2(DPKOH)] or with excess acetyl chloride to give [PtCl2Me2(DPK)]. Reaction of [PtMe2(DPK)] with methyl triflate in MeCN solution gave [PtMe3(NCMe)(DPK)][OTf], which reacted with more MeOTf in the presence of base to give [PtMe3{DPC(OMe)2}][OTf], where DPC(OMe)2 = κ3-NN′O-(2-C5H4N)2C(OMe)2. Hydrolysis of [PtF(NCMe)Me2(DPK)][BF4] gave [Pt{NHC(=O)Me}Me2(DPKOH)], which crystallized in partially protonated form as an unusual supramolecular polymer [Pt{NHC(=O)Me}Me2(DPKOH)]·0.5HBF4.Key words: platinum, oxidative addition, ketone, pyridyl.

Preparation of hydrido(vinyl)iridium(III) complexes from functionalized olefins by C—H activation

2006 ◽  
Vol 84 (2) ◽  
pp. 205-213 ◽  
Author(s):  
Bernd Papenfuhs ◽  
Thomas Dirnberger ◽  
Helmut Werner
Keyword(s):  
Key Words ◽  
Oxidative Addition ◽  
Metal Center ◽  
Addition Reactions ◽  
Phosphine Complexes

The four-coordinate iridium(I) precursor trans-[IrCl(N2)(PPh3)2] (1) reacts with functionalized olefins RCH=C(R′)C(O)R′′ by displacement of the dinitrogen ligand and oxidative addition of the C—H bond to the metal center to give six-coordinate hydrido(vinyl)iridium(III) complexes [IrH(Cl){κ2(C,O)-C(R)=C(R′)C(R′′)=O}(PPh3)2] (2–12) in good to excellent yields. The reaction of [IrH(Cl){κ2(C,O)-CH=CHC(Me)=O}(PPh3)2] (2) with AgClO4 affords the cationic compound [IrH{κ2(C,O)-CH=CHC(Me)=O}(PPh3)2]ClO4 (15), which in solution equilibrates with the uncharged isomers [IrH(OClO3){κ2(C,O)-CH=CHC(Me)=O}(PPh3)2] (15a and 15b). In contrast, five-coordinate [IrH{κ2(C,O)-CH=CHC(Et)=O}(PPh3)2]ClO4 (16), prepared from 3 and AgClO4, is stable and undergoes addition reactions with CO, PPh3, C2H4, CH3C≡CH, MeCN, and PhCN to give the six-coordinate complexes [IrH(L){κ2(C,O)-CH=CHC(Et)=O}(PPh3)2]ClO4 (17–22). The neutral hydrido(thiolato) compound [IrH(SPh){κ2(C,O)-CH=CHC(Et)=O}(PPh3)2] (23) was obtained on treatment of 21 with NaSPh. Key words: iridium, C—H activation, hydrido complexes, vinyl complexes, phosphine complexes.

Organoplatinum(IV) derivatized vinyl monomers and polymers prepared by oxidative addition

1996 ◽  
Vol 74 (11) ◽  
pp. 1983-1989 ◽  
Author(s):  
Sudhir Achar ◽  
Richard J. Puddephatt ◽  
John D. Scott
Keyword(s):  
Free Radical ◽  
Acrylic Acid ◽  
Key Words ◽  
Radical Polymerization ◽  
General Formula ◽  
Oxidative Addition ◽  
Free Radical Polymerization ◽  
Vinyl Monomers ◽  
Acryloyl Chloride ◽  
High Degree

Organoplatinum(IV) complexes of general formula [PtXMe2R(NN)], containing vinyl substituents, have been prepared by oxidative addition of RX, (RX = methyl 2-(bromomethyl)acrylate, 2-(bromomethyl)acrylic acid, 2-bromoethyl methacrylate, acryloyl chloride, and chloromethylstyrene), to [PtMe2(NN)], NN = 2,2′-bipyridine or 4,4′-di-tert-butyl-2,2′-bipyridine. Polymers with organoplatinum(IV) substituents have been prepared either by free radical polymerization of the organoplatinum(IV) derivatized monomers or by free radical polymerization of the organic monomers, followed by the oxidative addition of the C-X substituents of these polymers to [PtMe2(NN)]. In the latter method, it is generally not possible to metallate all the C—X bonds, but a high degree of platinum incorporation can be achieved. Key words: organoplatinum, polymer, oxidative addition, vinyl.

Cationic thiolate and selenolate complexes of platinum(IV)

2002 ◽  
Vol 80 (1) ◽  
pp. 41-45 ◽  
Author(s):  
Michael C Janzen ◽  
Michael C Jennings ◽  
Richard J Puddephatt
Keyword(s):  
Nmr Spectroscopy ◽  
Key Words ◽  
Oxidative Addition ◽  
Competitive Reaction ◽  
Methyl Group ◽  
X Ray ◽  
Group Transfer ◽  
Structure Determinations ◽  
Derivatives Of ◽  
Methyl Group Transfer

The reaction of the adamantanoid compounds [Hg4(EPh)6(L)4][ClO4]2 (E = S or Se, L = PEt3 or PPh3) with [PtMe2(bu2bpy)] (bu2bpy = 4,4'-di-tert-butyl-2,2'-bipyridine) occurs easily to give the first examples of cationic thiolate or selenolate derivatives of platinum(IV), [PtMe2(EPh)L(bu2bpy)][ClO4], and the addition is shown to occur with trans stereochemistry. The new complexes are characterized by NMR spectroscopy and when L = PEt3 by X-ray structure determinations. When L = PPh3, a competitive reaction leads to methyl group transfer from platinum to mercury to give MeHgEPh (E = S or Se).Key words: oxidative-addition, platinum, thiolate, selenolate, mercury.

The energetics of the oxidative addition of trisubstituted silanes to photochemically generated (η5-C5R5)Mn(CO)2

1996 ◽  
Vol 74 (11) ◽  
pp. 1959-1967 ◽  
Author(s):  
Bentley J. Palmer ◽  
Ross H. Hill
Keyword(s):  
Key Words ◽  
Kinetic Data ◽  
Addition Reaction ◽  
Solvent Molecule ◽  
Oxidative Addition ◽  
Isokinetic Temperature ◽  
Arrhenius Law ◽  
Isokinetic Relationship ◽  
Temperature Range ◽  
Oxidative Addition Reaction

The rates for the oxidative addition reaction of trisubstituted silanes (Et3SiH, Et2MeSiH, EtMe2SiH, Et2SiH2) to photochemically generated (η5-C5R5)Mn(CO)2 (R5 = H5, Me5, H4Me) species have been measured for the temperature range 70–125 K. The reactions were carried out in either neat silane or a 50/50, by volume, mixture of methylcyclohexane and silane. The activation energies, determined using Arrhenius law, varied from 2 to 35 kj/mol. The kinetic data fit an isokinetic relationship with an isokinetic temperature of 102 ± 6 K. The results are interpreted in terms of a variation in the loss of solvation prior to the oxidative addition. When the solvating molecule is methylcyclohexane, then loss of the solvent molecule precedes oxidative addition. In cases where solvation is by the silane, the incomplete loss of this silane precedes the oxidative addition. Key words: mechanism, oxidative addition, solvation.

Oxidative addition of a B—B bond by an iridium(I) complex: molecular structure of mer-cis-[Ir(PMe3)3Cl(Bcat)2]

1996 ◽  
Vol 74 (11) ◽  
pp. 2026-2031 ◽  
Author(s):  
Chaoyang Dai ◽  
Graham Stringer ◽  
Todd B. Marder ◽  
R. Thomas Baker ◽  
Andrew J. Scott ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Key Words ◽  
Oxidative Addition ◽  
Unit Cell ◽  
X Ray ◽  
Cell Dimensions ◽  
Unit Cell Dimensions ◽  
Group Environments

The B—B bond in B2Cat2 (cat = 1,2-O2C6H4) is readily activated by [Ir(PMe3)3Cl(COE)] (COE = η2-cyclooctene) (1) to yield a novel iridium(III) bis(boryl) complex mer-cis-[Ir(PMe3)3Cl(Bcat)2] (2). This complex is the first structurally characterized iridium bis(boryl) compound, and is the first metal bis(boryl) complex for which two distinct boryl group environments are observed in solution. Colourless crystals of 2 are monoclinic, P21/n, with unit cell dimensions a = 8.9638(7) Å, b = 32.197(2) Å, c = 9.3980(7) Å, and β = 90.385(2)°. Key words: iridium, boron, diboron, boryl, oxidative addition, X-ray structure, trimethylphosphine.

Some Problems in the Oxidative Addition and Binding of an Ethylene to a Transition Metal Center.

1987 ◽  
Vol 6 (4) ◽  
pp. 902-902
Author(s):  
Jerome Silestre ◽  
Maria Calhorda ◽  
Roald Hoffman ◽  
Page Stoutland ◽  
Robert Bergman
Keyword(s):  
Transition Metal ◽  
Oxidative Addition ◽  
Metal Center

Multislice imaging of gastrointestinal stromal tumors

2018 ◽  
pp. 3-14
Keyword(s):  
Computed Tomography ◽  
Key Words ◽  
Gold Standard ◽  
Gastrointestinal Stromal Tumors ◽  
Mesenchymal Tumors ◽  
Stromal Tumors ◽  
Preferential Localization ◽  
Multislice Imaging ◽  
Computed Tomography Diagnosis

Gastrointestinal stromal tumors (GIST) are the most common mesenchymal tumors of the digestive tract (1%). These tumors express the CD 117 in 95% of cases. The stomach is the preferential localization (70%). Diagnosis is difficult and sometimes late. Progress of imaging has greatly improved the management and the prognosis. Computed tomography (CT) is the gold standard for diagnosis, staging, and treatment follow-up. The increasing recognition of GIST’s histopathology and the prolonged survival revealed some suggestive imaging aspects. Key words: gastro-intestinal stromal tumors; computed tomography; diagnosis

METHODS OF CONSULTING ON STUDYING THE DEGREE OF MOISTURE SUPPLY OF SLOPE LANDS FOR AGRICULTURAL PRODUCTION IN AZERBAIJAN

2018 ◽  
Author(s):  
Prof.RAE Aliev Z.H.
Keyword(s):  
Key Words ◽  
Agricultural Production ◽  
Soil Ecology ◽  
Arable Soil ◽  
Clean Technology ◽  
Agricultural Product ◽  
Current Information ◽  
Moisture Supply ◽  
Managerial System

The current information on moisture and the temperature of the ground in managerial system by production to agricultural product necessary, in the first place, for taking the operative decisions at development ecological clean technology irrigation under growing agricultural cultures to achieve the maximum harvest. Key words: aerospace methods, COW, moisture, moisture test, arable, soil, ecology, vafer humidity, drill, graduation, tool, etc.

PELAKSANAAN HUKUM KEWARISAN ISLAM DI PENGADILAN AGAMA BANTEN

ALQALAM ◽  
2013 ◽  
Vol 30 (1) ◽  
pp. 158
Author(s):  
Yusuf Somawinata
Keyword(s):  
Key Words ◽  
Islamic Law ◽  
Survey Methods ◽  
Adopted Children ◽  
Inheritance Law ◽  
Library Research ◽  
The Ideal

This article aims at describing the obseroance of wasiat wajibah (compulsory bequeathment) in the Islamic court of Banten, analyzing the provision of the substitute heir and adopted children in the Compilation of  Islamic Law (KHI). In addition, the ideal laws to manage the innheritance rules in Indonesia. This article is library research by using doctrinal approach and using case study and survey methods. The data was, then, analyzed by using analytical descriptive and analytical correlative methods. The result showed that the observance of wasiat wajibah in the Islamic court of  Banten employed by judges is by using the Mawali Hazairin’s Doctrine. The criteria of the adoption of substitute heir and adopted children in the KHI is the attempts of Ulama and many judgees junst in giving legal justice and certainty to the society.   Key Words: Islamic Inheritance Law, Compilation of Islamic Law, Islamic court of  Banten

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