83095-83-4Relevant academic research and scientific papers
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
-
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.
Synthesis and application of 2,6-bis(trifluoromethyl)-4-pyridyl phosphanes: The most electron-poor aryl phosphanes with moderate bulkiness
Korenaga, Toshinobu,Ko, Aram,Uotani, Kotaro,Tanaka, Yuki,Sakai, Takashi
, p. 10703 - 10707 (2012/01/04)
The poor will be rich: BFPy phosphanes (see scheme) mimic the electronic and steric characters of P(C6F5)3 and PPh 3, respectively. These novel ligands showed a large ligand acceleration effect on Stille coupling, the Rh-catalyzed 1,2-addition of aryl boronic acid to unactivated ketones and the asymmetric arylation of N-tosylimine using phenylboronic acid. Copyright
Novel reactivity aspects of cis-bis(1-alkenyl)platinum(II) compounds of the type Pt(CH2(CH2)nCHCH2) 2L2 (where L2 = dppp, dppe, dppm and n = 1, 2)
Sivaramakrishna, Akella,Moss, John R.,Su, Hong
, p. 3345 - 3350 (2011/02/16)
We describe the synthesis, structure and reactivity of novel bis(1-alkenyl)platinum(II) complexes, Pt[CH2(CH2) nCHCH2]2L2 (where L2 = dppp, dppe, dppm and n = 1, 2). The stability of the title complexes with the different ligands is discussed. The steric, chelating and electronic properties of the ligands have a significant impact on the structure as well as on the reactivity of the complexes. Novel reactions with elemental sulfur and carbon dioxide are described and discussed.
The reactivity of dinuclear platina-β-diketones with phosphines: Diacetylplatinum(II) complexes and mononuclear platina-β-diketones
Albrecht, Christian,Wagner, Christoph,Steinborn, Dirk
, p. 2858 - 2866 (2009/05/30)
Addition of mono- and bidentate phosphines or of AsPh3 to the platina-β-diketone [Pt2{(COMe)2H}2(μ- Cl)2] (1) followed by the addition of NaOMe at -70°C resulted in the formation of diacetyl platinum(II) complexes cis-[Pt(COMe)2L 2] (L = PPh3, 2a; P(4-FC6H4) 3, 2b; PPh2(4-py), 2c; PMePh2, 2d; AsPh 3, 2d) and [Pt(COMe)2(Lcombining double inverted breveL)] (Lcombining double inverted breveL = dppe, 3b; dppp, 3c), respectively. The analogous reaction with dppm afforded the dinuclear complex cis-[{Pt(COMe) 2}2(μ-dppm)2] (4) that reacted in boiling acetone yielding [Pt(COMe)2(dppm)] (3a). The reactions 1 → 2/3 were found to proceed via thermally highly unstable cationic mononuclear platina-β-diketone intermediates [Pt{(COMe)2H}L 2]+ and [Pt{(COMe)2H}(Lcombining double inverted breveL)]+, respectively, that could be isolated as chlorides for Lcombining double inverted breveL = dppe (5a) and dppp (5b). The reversibility of the deprotonation of type 5 complexes with NaOMe yielding type 3 complexes was shown by the protonation of the diacetyl complex 3b with HBF4 yielding the platina-β-diketone [Pt{(COMe)2H}(dppe)](BF 4) (5c). All compounds were fully characterized by means of NMR and IR spectroscopies, and microanalyses. X-ray diffraction analysis was performed for the complex cis-[Pt(COMe)2(PPh3)2] ·H2O·CHCl3 (2a·H2O· CHCl3).
