14873-92-8Relevant academic research and scientific papers
Cis-Dichloridobis(diethyl sulfide-κS)platinum(II) at 295 and 150 K
Hansson, Christian
, p. m361-m363 (2007)
The title compound, cis-[PtCl2(C4H10S)2], crystallizes in the space group P21/n with pseudo-square-planar coordination geometry. The orientation of the ethyl groups on the S atoms is staggered with respect to the coordination plane, giving the complex approximate C 2v symmetry. The complex does not form dimeric packing units with short Pt...S intra-dimeric distances as seen in some related complexes, but instead displays C - H...Cl inter-actions in three dimensions. These C - H...Cl - Pt contacts are compared with those of related compounds reported in the Cambridge Structural Database, which show a frequency maximum in the range 120-170° for the C - H...Cl angle. International Union of Crystallography 2007.
Some mono- and binuclear platinacyclopentane complexes: A comparative kinetic study of reaction of ethyl iodide with platina(II)cyclopentane and dimethylplatinum(II) complexes
Rashidi, Mehdi,Esmaeilbeig, Ahmad R.,Shahabadi, Nahid,Tangestaninejad, Shahram,Puddephatt, Richard J.
, p. 53 - 61 (1998)
The reaction of Li(CH2)4Li with [PtCl2(SEt2)2] yielded an unstable complex, probably [{Pt(CH2CH2CH2CH2)(μ-SEt 2)}2], 1. Complex 1 reacts with bis(diphenylphosphino)methane, dppm, and forms [{Pt(CH2CH2CH2CH2)(μ-dppm)} 2], 2. Complex 2 has been fully characterized using multinuclear NMR and FAB mass spectroscopies and shown to be fluxional in solution. The bright red platinacyclopentane complex [Pt(CH2CH2CH2CH2)(bpy)], 3, in which bpy=2,2′ bipyridyl, has been prepared by reaction of 1 with bpy. In a comparative kinetic study, it was demonstrated that at different temperatures, EtI reacted 2.2-2.6 times faster with the platina(II)cyclopentane complex 3 than with the dimethyl analogue [PtMe2(bpy)].
Detailed mechanistic information on methane elimination from a methyl(hydrido)platinum(IV) complex. Relevance for the mechanism of methane activation
Fekl, Ulrich,Zahl, Achim,Van Eldik, Rudi
, p. 4156 - 4164 (1999)
The kinetics of methane reductive elimination from both isomers of the methyl(hydrido)-platinum(IV) complex [Pt(H)(CH3)2(BPMA)]+ (BPMA = bis(pyridylmethyl)amine) were studied by 1H NMR spectroscopy. The application of high-pressure techniques enabled the determination of the activation volume for methane elimination (+6 cm3/mol for the cis isomer, ca. +8 cm3/mol for the trans isomer). The low activation volume together with results on the rate and stereochemistry of deuterium incorporation into one methyl group of the cis isomer provides the basis for a suggested mechanism that involves five-coordinate platinum as a steady-state intermediate.
Intramolecularly stabilized 1,4-phenylene-bridged homo- and heterodinuclear palladium and platinum organometallic complexes containing N,C,N-coordination motifs; η1-SO2 coordination and formation of an organometallic arenium ion complex with two Pt-C σ-Bonds
Steenwinkel, Pablo,Kooijman, Huub,Smeets, Wilberth J. J.,Spek, Anthony L.,Grove, David M.,Van Koten, Gerard
, p. 5411 - 5426 (1998)
The new ligand precursors [1-(Me3Si)-4-(R){C6(CH2NMe2) 4-2,3,5,6}] (2, R = Me3Si; 3, R = H) have been used for the preparation of ionic 1,4-phenylene-bridged bispalladium(II) and palladium(II)-platinum(II) complexes [1-{M(MeCN)}-4-{M′(MeCN)}{C6(CH2NMe 2)4-2,3,5,6}]-(BPh4)2 (5b, M = M′ = Pd; 10, M = Pd, M′ = Pt). Lithium-halogen exchange of the new ligand precursor C6Br2(CH2NMe2)4-2,3,5,6, 11, generates a presumably polymeric organodilithium reagent, 12, which in a transmetalation reaction with [PtCl2(Et2S)2] affords the 1,4-phenylene-bridged bisplatinum complex [1,4-(PtCl)2{C6(CH2NMe2) 4-2,3,5,6}], 13. Reaction of colorless 13 with SO2 affords the unique orange bis-SO2 adduct [1,4-{PtCl(η1-SO2)}2{C6(CH 2NMe2)4-2,3,5,6}], 16, of which an X-ray crystal structure has been determined. The ionic derivative [1,4-{Pt(MeCN)}2{C6(CH2NMe2) 4-2,3,5,6}](BPh4)2, 14b, obtained by reaction of 13 with AgOTf in MeCN followed by addition of NaBPh4, has been the subject of an X-ray crystal structure determination. The X-ray molecular structures of 5b, 10, and 14b have been determined and show intramolecular M?M distances of ca. 6.5 A?. The bistriflate complex [1,4-{Pt(MeCN)}2{C6(CH2NMe 2)4-2,3,5,6}](OTf)2,14a, has also been used for the synthesis of the organometallic polymer {[1,4-{PtI(μ-I)}2{C6(CH2N(H)Me 2)4-2,3,5,6}]n}-(OTf)2n, 24. Triflate complex 14a slowly reacts with iodomethane to afford the dark red air-stable crystalline complex [1,4-{PtI}2{C6Me-1-(CH2NMe2) 4-2,3,5,6}](OTf), 23. The X-ray molecular structure of 23 shows it to be a unique arenium ion species with two para-oriented σ-bonded iodoplatinum substituents.
9,10-dihydroplatinaanthracenes with aromatic diimine ligands: Syntheses and spectroscopic and computational studies of new luminescent materials
De Crisci, Antonio G.,Lough, Alan J.,Multani, Kanwarpal,Fekl, Ulrich
, p. 1765 - 1779 (2009/02/01)
9,10-Dihydroplatinaanthracenes with aromatic nitrogen ligands were synthesized, derived from 2,2′-bipyridine, 4,4′-dichloro-2,2′- bipyridine, 4,4′-dimethoxy-2,2′-bipyridine, 4,4′- bis(dimethylamino)-2,2′-bipyridine, 4,4′-di-tert-butyl-2,2′- bipyridine, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, and 2,2′-biquinoline. For comparison purposes, the N,N,N′,N′-tetramethylethylenediamine- derived compound was also obtained. A single-crystal X-ray structure determination was carried out on [H2C(C6H 4)2]Pt(2,9-dimethyl-1,10-phenanthroline), revealing a pronounced boat conformation of the metallacyclic ring. The diimine-derived compounds are highly luminescent in the solid state at room temperature, as well as in frozen solution. The luminescent complexes are easily prepared by ligand substitution from the new organometallic platinum precursor {[H 2C-(C6H4)2]Pt(SEt2)} n (n = 2, 3). Spectroscopic data are provided on absorbance and emission in the UV-visible range. In order to obtain insight into orbital energies and the tunability of the optical properties, electrochemical data, as well as DFT and TD-DFT data, were obtained. The lowest-energy absorbances are due to charge transfer from orbitals located largely on the electron-rich metallacyclic ligand with some coefficient on Pt into π* orbitals of the diimine. Computations suggest that the low-energy bands mostly originate from charge transfer from the HOMO-2, HOMO-1, and HOMO to the LUMO (rarely LUMO+1 and LUMO+2) molecular orbitals. Emission maxima range from 536 to 690 nm.
Nucleophilic Discrimination and the trans Effect. The Kinetics of Displacement of X from trans-n- (L=Me2SO, Et2S, PMe3, PEt3, PPh3, or AsEt3; X=Cl, n=1; X=MeOH, n=0) by Neutral and Anionic Nucleophiles
Tobe, Martin L.,Treadgold, Andrew T.
, p. 2347 - 2352 (2007/10/02)
The kinetics of the reaction trans-n- + L' trans-n'- + X (X=Cl-, n=1, L=Me2SO, Et2S, PMe3, PEt3, PPh3, or AsEt3, L'=pyridine (py), Me2S, Et2S, PPh3, Me2SO, thiourea (tu), or NNN'N'-tetramethylthiourea (tmtu), n'=0; L'=Cl-, Br-, I-, or SCN-, n'=1; X=MeOH, n=0, L'=Cl-, Br-, I-, or SCN-, n'=1) have been studied in 95percent methanol and 5percent water at 25 deg C.The second-order rate constants, k2, for the anionic substrates do not follow the usual dependence upon n0Pt, the anionic nucleophiles being much less reactive than predicted.A new nucleophilicity scale, based on - as standard substrate, does give linear relationships for all the anionic substrates.The relationship between the nucleophilic discrimination and the nature of the trans ligand is discussed.
Fast Cis-Trans Isomerization of Square-Planar Bis(diethyl sulfide)platinum(II) Complexes. Reaction of cis-Dichlorobis(diethyl sulfide)platinum(II) with Mesityllithium
Tobita, Hiromi,Habazaki, Hiroki,Ogino, Hiroshi
, p. 797 - 799 (2007/10/02)
Reaction of cis- with a slight excess of mesityllithium in benzene-ether mixture afforded trans- (Mes=2,4,6-trimethylphenyl; SEt2=diethyl sulfide) as a major product.When mesityllithium reagent containing lithium bromide was used, trans- was obtained.Acceleration of cis-trans isomerization in the presence of mesityllithium was observed.
Redox, ligand-exchange, oligomerization, and hydrosilation chemistry of trans-dichloro(ethylene)(phenazine)platinum
Siedle,Mann,Bohling,Filipovich,Toren,Palensky,Newmark,Duerst,Stebbings,Mishmash,Melancon
, p. 2216 - 2223 (2008/10/08)
A series of compounds of the type trans-(amine)PtCl2(C2H4) (amine = phenazine, quinoxaline, pyrazine, phenazine N-oxide, 2,6-dimethylpyrazine, tetramethylpyrazine, acridine) was prepared by displacement of chloride from PtCl3(C2H4)-. (phenazine)PtCl2(C2H4) is an effective hydrosilation catalyst. It reacts with L (L = styrene, Ph3P, Ph3As) to form (phenazine)PtCl2L and (phenazine)[PtCl2L]2. Pyrolysis leads to (phenazine)2(PtCl2)2(C2H4). Reduction of (phenazine)PtCl2(C2H4) to form [(phenazine)PtCl2(C2H4)]2 -·, whose ESR spectrum is discussed, was found by double-potential-step chronocoulometry to proceed by an ECE mechanism. The platinum-catalyzed reduction by hydrogen yields H[(phenazine)PtCl2(C2H4)]2. Reduction by silanes, R3SiH, in CHCl3 produces H3[(phenazine)PtCl2(C2H4)] 3PtCl3. Characterization of these compounds by X-ray photoelectron spectroscopy is discussed.
