14647-25-7Relevant articles and documents
Chemistry of Platinum Sulphido-complexes. Part 3. Crystal and Molecular Structure of Tetrasulphidoplatinum(II) and a Study of its Bonding and Reactions
Briant, Clive E.,Calhorda, Maria J.,Hor, T. S. Andy,Howells, Nigel D.,Mingos, D. Michael P.
, p. 1325 - 1330 (1983)
The structure of has been determined by single-crystal X-ray techniques using deffractometer data.The compound crystallises in the monoclinic space proup P21/a, with four molecules in a cell of dimensions a=9.736(3), b=30.964(7), c=9.806(5) Angstroem, and β=117.81(4) deg.Least-squares refinement of the structure led to a final R value of 0.043 using 3292 observed intensities.The complex is approximately square planar and the tetrasulphido-ligand behaves as a dianionic chelating ligand.The resultant PtS4 ring adopts an approximately C2 conformation.The central S-S bond is 0.046 Angstroem shorter than the outer S-S bonds .A molecular orbital analysis of the bonding in this and related complexes has been used to interpret this geometric feature.
The Nature of Pt(Ph2PCH2CH2PPh2) . A Platinum(I)-Platinum(I) Dimer containing Bridging Cyclometallated 1,2-Bis(diphenylphosphino)ethane; X-Ray Crystal Structure
Arnold, Dennis P.,Bennett, Martin A.,Bilton, Malcolm S.,Robertson, Glen B.
, p. 115 - 116 (1982)
Single-crystal X-ray structural analysis of a complex of empirical formula (dppe = Ph2PCH2CH2PPh2) formed by heating in methanol shows that it should be formulated as >2 and that it contains cyclometallated dppe ligands bridging a PtI-PtI bond.
Synthesis of rhenium-platinum complexes bearing carbaborane ligands and their unusual dynamic behavior
Ellis, Dianne D.,Jelliss, Paul A.,Stone, F. Gordon A.
, p. 2113 - 2122 (2000)
Treatment of Cs[3,3,3-(CO)3-closo-3,1,2-ReC2B9H 11]1 with [Pt(NCMe)2{Ph2P(CH2)2PPh 2}][BF4]2 yielded [3,3,3-(CO)3,3,8-(Pt{Ph2P(CH2) 2PPh2})-8-(μ-H)-closo-3,1,2-ReC2B 9H10][BF4] 2b as the sole product. The cation of salt 2b is a bimetallic species with a Re-Pt bond bridged by a nido-7,8-C2B9H11 ligand pentahapto coordinated to the rhenium and with the β-B-H bond in the ligating CCBBB ring of the carbaborane cage forming a 3-centre 2-electron B-HPt bond. Deprotonation of 2b with strong bases gives an isomeric mixture of the complexes [3,3,3-(CO)3-3,n-(Pt{Ph2P(CH2)2PPh 2})-closo-3,1,2-ReC2B9H10] 3a (n = 4), 3b (n = 8). The isomers are readily separated and the proportion of 3a to 3b formed is solvent- as well as base-dependent. In THF solutions of 2b afford a 1:3:1 equilibrium mixture of 2b, 3a, and 3b. Refluxing THF solutions of 1 with [Pt(H)(THF)(PEt3)2[BF4] for several days yields a separable mixture of the isomers [3,3,3-(CO)3-3,n)-{Pt(PEt3) 2}-closo-3,1,2-ReC2B9H10] 4a (n = 4), 4b (n = 8). The same reactants, when stirred together in CH2Cl2 at ambient temperatures, give 4a and [3,3,3-(CO)3-3,8-{Pt(H)(PEt3)}-8-(μ-H)-closo-3,1,2-ReC 2B9H10] 5. Complex 4a, not 5, is the precursor to 4b, the interconversion occurring at elevated temperatures in solution by an intramolecular exchange of B-Pt a bonds between α-B and β-B vertices in the coordinating CCBBB face of the cage. Treatment of 1 with [Pt(Me)(THF)-(PMe2Ph)2][BF4] at room temperature initially gives [3,3,3-(CO)3-3,4-{Pt(PMe2Ph) 2}-closo-3,1,2-ReC2B9H10] 6a. However, 6a isomerizes in CH2Cl2 solutions at ambient temperatures to give a 1:1 mixture of 6a and [3,3,3-(CO)3-3,8-{Pt(PMe2Ph) 2}-closo-3,1,2-ReC2B9H10] 6b. The NMR data (1H, 13C, 11B and 31P) for the new complexes are discussed. The Royal Society of Chemistry 2000.
Triphenylene based metal-pyridine cages
Berton, Giacomo,Lorenzetto, Tommaso,Borsato, Giuseppe,Sgarbossa, Paolo,Santo, Claudio,Visentin, Fabiano,Fabris, Fabrizio,Scarso, Alessandro
supporting information, (2019/10/02)
C3-symmetric pyridine containing tris-benzyl-O-substituted hexahydroxytriphenylene derivatives were prepared and used in combination with square-planar Pd(II) and Pt(II) complexes for the self-assembly of molecular cages in solution. The formation of a trigonal bipyramid M3L2 cage was demonstrated by multinuclear NMR analyses and pseudo 2D DOSY experiments and supported by semi-empirical calculations.
Stereochemical Effects on Platinum Acetylide Two-Photon Chromophores
Shelton, Abigail H.,Valandro, Silvano R.,Price, Randi S.,Dubinina, Galyna G.,Abboud, Khalil A.,Wicks, Geoffrey,Rebane, Aleksander,Younus, Muhammad,Schanze, Kirk S.
, p. 9382 - 9393 (2019/11/03)
A series of cis-platinum(II) acetylide complexes containing two-photon-absorbing chromophores have been synthesized and characterized to explore the effects of stereochemistry on the nonlinear absorption properties. The molecules feature 4-(phenylethynyl)phenylethynylene (PE2), diphenylaminofluorene (DPAF), and benzothiazolylfluorene (BTF) ligands. The photophysical properties were investigated under one- and two-photon conditions and compared to the known trans analogues via UV-visible absorption, photoluminescence, femtosecond and nanosecond transient absorption (TA), nanosecond z-scan, and femtosecond two-photon absorption (2PA). The bent cis complexes exhibit blue shifts in the absorption, emission, femtosecond, and nanosecond TA spectra along with lower molar extinction coefficients and lower phosphorescence yields relative to the trans complexes suggesting less efficient Pt-induced spin-orbit coupling and intersystem crossing in the cis configuration. The cis chromophores are noncentrosymmetric and therefore show dipolar behavior with a pronounced 2PA in the 0-0 transition of the S0 → S1 band, while the trans complexes show quadrupolar behavior with a forbidden 0-0 transition. In the S0 → Sn region, both cis and trans complexes show intense two-photon-absorption bands (up to 3700 GM by the peak cross section for cis-BTF) which contain a significant contribution from the excited state absorption (S1 → Sn). All six complexes exhibit comparable nonlinear absorption response with a significant contribution from triplet-triplet absorption that slightly favors trans complexes but is more strongly dependent upon the structure of the π-conjugated chromophore.
The structure of the photochromic compounds and its synthetic method
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Paragraph 0030; 0060-0063, (2017/02/02)
The invention relates to four photochromic compounds having cyclic structures and a synthesis method of the photochromic compounds. The synthesis method of the four compounds all of which have the cyclic structures comprises the following steps: (1) carry
Combinatorial approach to chiral tris-ligated carbophilic platinum complexes: Application to asymmetric catalysis
Pradal, Alexandre,Gladiali, Serafino,Michelet, Veronique,Toullec, Patrick Y.
supporting information, p. 7128 - 7135 (2014/06/09)
A straightforward methodology for the synthesis of libraries of chiral tris-ligated cationic platinum complexes and their in situ evaluation as asymmetric carbophilic catalysts in a model domino hydroarylation/cyclization reaction of a 1,6-enyne was developed. A catalyst-generation process based on a combination of a monodentate and a bidentate phosphorus ligand allowed the formation of 108 chiral complexes. One-pot screening of the stereoinduction obtained with this library in a test domino addition/cyclization reaction validated this approach and stressed the key role played by the monodentate ligand partner in obtaining high enantioselectivities. In the case of two challenging substrate/nucleophile combinations, the combinatorial approach resulted in a significant gain in enantioselectivity.
Bismuth-halide oxidative addition and bismuth-carbon reductive elimination in platinum complexes containing chelating diphosphine ligands
Nabavizadeh, S. Masoud,Niroomand Hosseini, Fatemeh,Nejabat, Negar,Parsa, Zahra
, p. 13480 - 13489 (2014/01/06)
Reaction of BiX3 (X = Cl, Br, I) with [PtMe2(P-P)], (1a, P-P = dppm; 1b, P-P = dppe), occurs easily to yield a mixture of platinum(II) complexes [PtMeX(P-P)], 2, and [PtX2(P-P)], 3, and the binuclear complex [Pt2Me2(μ-X)(μ-dppm) 2]X, 4. On the basis of 31P NMR and UV-vis spectroscopy, a mechanism is proposed in which the rate determining step is conversion of the yellowish Pt(II)-BiX3 adduct BiI3·[PtMe 2(dppm)], A, into the Pt(IV)-Bi(III) intermediate [PtMe 2(BiX2)X(P-P)], IM1. Density functional theory (DFT) studies suggest that intermediate IM1 may be formed in acetone solution which undergoes the Bi-C reductive elimination process before formation of complexes 2 and 3. The structures of intermediates IM1 were theoretically determined using DFT calculations. In dilute acetone solution, as monitored by UV-vis spectroscopy, the oxidative addition processes follow first order kinetics. The overall reaction is slower for heavier halide.
Thiosaccharinate binding to palladium(II) and platinum(II): Synthesis and molecular structures of sulfur-bound complexes [M(κ1-tsac) 2(κ2-diphosphane)]
Al-Jibori, Subhi A.,Al-Jibori, Mohamed H.S.,Hogarth, Graeme
, p. 117 - 123 (2013/05/22)
Palladium(II) and platinum(II) thiosaccharinate complexes [M(κ1-tsac)2{κ2-Ph 2P(CH2)nPPh2}] (M = Pd, Pt; n = 1-4) have been prepared, palladium complexes from reaction of [Pd(tsac) 2]·H2O with diphosphanes and platinum complexes from addition of thiosaccharin to [PtCl2{κ2-Ph 2P(CH2)nPPh2}] in the presence of triethylamine. All complexes have been fully characterized and the crystal structures of [Pd(κ1-tsac)2(κ2- dppp)] (n = 3) and [Pt(κ1-tsac)2(κ 2-dppm)] (n = 1) have been determined confirming that thiosaccharinate ligands are S-bound. The larger ring complexes (n = 3, 4) are fluxional in solution being attributed to the conformational flexibility of the diphosphane backbones The bis(diphosphane) complexes, [M(κ1- tsac)2(κ1-dppm)2] (M = Pd, Pt), have also been prepared upon treatment of [Pd(tsac)2]·H2O with two equivalents of dppm or addition of thiosaccharin to [Pt(κ2-dppm)2]Cl2 in the presence of triethylamine in which the diphosphanes bind in a monodentate fashion. Both are highly fluxional in solution, changes in the 31P{1H} NMR spectra as a function of temperature being interpreted as the exchange of bound and unbound phosphorus atoms.
Synthesis and structure of gold and platinum menthyl complexes
Zuzek, Ashley A.,Reynolds, Samantha C.,Glueck, David S.,Golen, James A.,Rheingold, Arnold L.
, p. 1812 - 1817 (2011/05/12)
A Grignard reagent derived from (-)-menthyl chloride has been reported to be a 1:1 mixture of menthyl magnesium chloride and neomenthyl magnesium chloride, which do not interconvert. Addition of an excess of this reagent to Au(PPh3)(Cl) or Pt(dppe)Cl2 gave Au(PPh3)(Men) (1) and Pt(dppe)(Men)(Br) (2), respectively. Crystallographic studies of these first well-characterized transition metal menthyl complexes showed that the menthyl group adopts a conformation with all three substituents in equatorial positions. NMR spectroscopic data for 2 showed that menthyl has a large trans influence, comparable to other alkyl groups. Decomposition of 1 in CDCl 3 gave Au(PPh3)(Cl) and a mixture of menthyl chloride and neomenthyl chloride, while 2 formed the halide complexes Pt(dppe)Cl2, Pt(dppe)Br2, and Pt(dppe)(Br)(Cl) and a mixture of 2-menthene and 3-menthene.
