37410-35-8Relevant academic research and scientific papers
Photochemical Synthesis of cis,trans,cis-1,2,3,4-Tetrakis(diphenylphosphanyl)buta-1,3-diene and Its Metal Coordination
Prock, Johannes,Ehrmann, Katharina,Viertl, Wolfgang,Pehn, Richard,Pann, Johann,Roithmeyer, Helena,Bendig, Marvin,Rodríguez Villalón, Alba,Kopacka, Holger,Dumfort, Alexander,Oberhauser, Werner,Clausing, Simon T.,Kn?r, Günther,Brüggeller, Peter
, p. 4962 - 4971 (2018)
The new bis(bidentate) tetraphosphane cis,trans,cis-1,2,3,4-tetrakis(diphenylphosphanyl)buta-1,3-diene (dppbd) (7) was obtained by applying a photochemical synthetic protocol. The key step of the photochemical reaction consisted of an intramolecular [2+2] cycloaddition involving a C–C double and triple bond of the Pt-dimer species of the formula [Pt2Cl4(dppa)(trans-dppen)] (2) {dppa = 1,2-bis(diphenylphosphanyl)acetylene and dppen = 1,2-bis(diphenylphosphanyl)ethene} leading to [Pt2Cl4(dppbd)] (5). The asymmetrically bridged precursor complex 2 was obtained by combinatorial chemistry. Single crystal X-ray structure analyses of 2 and 5 proved that the intramolecular photochemical reaction occurred. Cyanolysis of 5 gave 7, which was oxidized to dppbdO4 (8). Compounds 7, 8, and the PdII dimer complex [Pd2Cl4(dppbd)] (9) were characterized in the solid state by a single-crystal X-ray structure analysis. Interesting photophysial properties emerged from the UV/Vis spectra acquired for 7 and the dimer Os complexes meso-Δ,Λ/Λ,Δ-[Os2(bpy)4(dppbd)](PF6)4 (10) and rac-Δ,Δ/Λ,Λ-[Os2(bpy)4(dppbd)](PF6)4 (11).
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.
Palladium(II) and platinum(II) complexes of cis-1,2-bis(diphenylphosphino)ethene: completely planar structures due to π bonding in the case of platinum(II)
Oberhauser, Werner,Bachmann, Christian,Brueggeller, Peter
, p. 35 - 44 (2008/10/08)
Several novel Pd(II) and Pt(II) complexes contaning the diphos ligand cis-1,2-(diphenylphosphino)ethene (cis-dppen) have been prepared and characterized by X-ray diffraction methods. NMR spectroscopy (195)Pt{(1)H}, (31)P{(1)H}), IR spectroscopy, elemental analyses and melting points. In contrast to the former reported and directly available compounds [PtCl2(cis-dppen)] (1) and [Pd(cis-dppen)2](BPh4)2 (3), an intermediate is formed in the synthesis of [PtCl2(cis-dppen)] (2). It is shown that this intermediate is of type [Pt(cis-dppen)2](2+). Both 2 and [Pt(cis-dppen)2](BPh4)2 (4) are fully characterized by X-ray structure analyses: 2: monoclinic, P21/m, a=8.507(2), b=18.236(4), c=11.205(2)?, β=105.25(3)°, R=0.052 for 3070 observed reflections (I>3σ(I)); 4: monoclinic, P21/c, a=10.718(2), b=17.283(3), c=24.549(5)?, β=99.25(3)°, R=0.028 for 5588 observed reflections (I>3σ(I)). In 2 and 4 the Pt atoms show square-planar coordinations, where in both casesthe ethene bridges are stricly coplanar with the coordination planes. T his gives strong evidence of a πbonding interaction including the ethene bridges. Replacement of the chlorides in 1 and 2 by 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen) leads to the square-planar compounds [Pd(cis-dppen)(bipy)](BPh4)2 (5), [Pt(cis-dppen)(bipy)](PF6)2 (6), [Pd(cis-dppen)(phen)] (7) and [Pt(cis-dppen)(phen)](BF4)2 (8). Similar reaction with NO2(1-) produce [Pd(NO2)2(cis-dppen)] (9), [Pt(NO2)2(cis-dppen)] (10) and [PtCl(NO2)(cis-dppen)] (11). From Pd(CN)2 and cis-dppen [Pd(CN)2(cis-dppen)] (12) is formed. The stability and reactivity of complexes 1-12 are discussed with respect to the known non-planar X-ray structures of [PtCl2(dppe)], where dppe is 1,2-bis(diphenylphosphino)ethane, and [Ni(cis-dppen)2](ClO4)2.
Luminescent diphosphine dithiolate complexes of platinum(II): Synthesis, characterization, and structure
Bevilacqua, Joanne M.,Zuleta, Juan A.,Eisenberg, Richard
, p. 258 - 266 (2008/10/08)
The synthesis, characterization, and emission properties of a series of Pt(diphosphine)(dithiolate) complexes are reported. Diphosphine ligands include 1,2-bis(diphenylphosphino)ethane (dppe), 1,2-bis(diphenylphosphino)ethylene (dppv), 1,2-bis(diphenylphosphino)benzene (dppb), 1,2-bis(dicyclohexylphosphino)ethane (chpe), bis(diphenylphosphino)methane (dppm), 1,2-bis(dimethoxyphosphino)ethane (pompom), triphenylphosphine (PPh3), dimethylphenylphosphine (PMe2Ph), tricyclohexylphosphine (PCy3), triphenyl phosphite (P(OPh)3), and triisopropyl phosphite (P(O-i-Pr)3). Dithiolate ligands include maleonitriledithiolate (mnt) and 1-(ethoxycarbonyl)-1-cyanoethylene-2,2-dithiolate (ecda). The complexes are readily synthesized by the addition of the diphosphine ligand to Pt(COD)(dithiolate). On the basis of characterizations using NMR and infrared spectroscopies, all of the complexes are assigned square planar coordination geometries with varying degrees of distortion determined by ligand steric and electronic effects. The assignment of square planar coordination is confirmed by single crystal structure determinations of Pt(dppe)(mnt) (1a) and Pt(dppb)(mnt) (3a). Pink crystals of Pt(dppe)(mnt) (1a) (C30H24N2P2PtS2) are monoclinic, space group P21/n (No. 14), with a = 11.491(4) ?, b = 12.484(2) ?, c = 19.822(7) ?, β = 91.34(1)°, V = 2842.90 ?3, Z = 4, and final R = 0.029 (Rw = 0.031) for 4793 unique reflections. Orange crystals of Pt(dppb)(mnt) (3a) (C34H24N2P2PtS2) are monoclinic, space group P21/n (No. 14), with a = 10.050(7) ?, b = 19.301(3) ? c, = 15.800(6) ?, β = 94.36(6)°, V = 3056.28 ?3, Z = 4, and final R = 0.030 (Rw = 0.036) for 5576 unique reflections. The average Pt-S (2.299(7) ? for 1a and 2.301(2) ? for 3a) and Pt-P (2.257(2) ? for 1a and 2.256(7) ? for 3a) bond distances in each structure agree well with previously reported structural results. The metrical parameters of the mnt chelate ring indicate some degree of metal-ligand delocalization in both structures. The 31P NMR spectra of the phosphines resonances for all of the complexes show platinum satellites (1JPt-P = 1100-2500 Hz). In addition, the ecda complexes exhibit complex second-order coupling patterns, arising from the asymmetry of the ecda ligand. All of the complexes exhibit strong emission in the solid state and in frozen glasses at 77 K. Emission spectra are structured for the mnt complexes and broad and featureless for the ecda complexes. Solid-state emission lifetimes at 77 K are in the microsecond range.
UEBER DEN MECHANISMUS DER LICHT-INDUZIERTEN ELIMINIERUNG DES BIPHENYL-SYSTEMS AUS cis-BIS(PHENYL)PLATIN(II)-VERBINDUNGEN
Klotzbuecher, Rainer,Brune, Hans Albert
, p. 399 - 407 (2007/10/02)
We report the light-induced reductive elimination of the biphenyl system from compounds of the types bis(phenyl)2-1,2-bis(diphenylphosphano)ethan>platinum(II), bis(phenyl)2-cis-1,2-bis(diphenylphosphano)ethene>platinum(II) and bis(phenyl)2-1,2-bis(diphenylphosphano)benzene>platinum(II) with substituents in the platinum-bound phenyl rings.The elimination proceeds via a concerted reaction mechanism without any observable free radical involvement.
Preparation and Spectroscopic Properties of Cyclohexyneplatinum(0) Complexes Containing Ditertiary Arylphosphines and of Their Protonation Products
Bennett, Martin A.,Rokicki, Andrzej
, p. 1307 - 1318 (2007/10/02)
Cyclohexyneplatinum(0) complexes Pt(C6H8)(P-P) and Pt(C6H8)(PMePh2)2 have been prepared by displacement of triphenylphosphine from Pt(C6H8)(PPh3)2.Like the known compound containing Ph2PCH2CH2PPh2, these complexes are readily protonated by both strong and weak acids (HY) to give η1-cyclohexen-1-yl-platinum(II) complexes PtY(C6H9)(P-P) (Y=Cl, SPh, O2CMe, CH2CN, OMe, OH).An excess of HCl rapidly cleaves the Pt-C6H9 bond giving PtCl2(P-P) complexes identical with those made from PtCl2(cycloocta-1,5-diene) and P-P.The methoxo complexes react rapidly with water to give the hydroxo complexes and with CO to give methoxycarbonyl complexes Pt(CO2Me)(C6H9)(P-P).The i.r., 1H and 31P n.m.r. spectra of the new complexes are reported and trends in the 31P chemical shifts (δP) and in the 195Pt-31P coupling constants (1JPt,P) are compared with those reported in the literature for related systems.
Co-ordination Chemistry of Higher Oxidation States. Part 2. Neutral and Cationic Complexes of Platinum(IV) with Bi- and Multi-dentate Ligands
Gulliver, David J.,Levason, William,Smith, Kenneth G.
, p. 2153 - 2158 (2007/10/02)
Octahedral platinum(IV) complexes have been prepared by oxidation of with halogen (X2) in CCl4.The amine, phosphine, and arsine complexes are very stable thermally and in solution, but the stibines decompose slowly at ambient temperature and immediately in solution.Decomposition of in solution gives , Me2Sb(Cl2)(CH2)3Sb(Cl2)Me2, and other products.Several unstable complexes have been prepared, which lose iodine very easily and are partially dissociated in solution.Chlorine oxidation of produced trans-Cl2, but for L'-L' = o-C6H4(AsPh2)2 or cis-Ph2AsCH=CHAsPh2 the product was and oxidised ligand.The complex gave on chlorine oxidation in solution, but Pt(L-L)2Cl4 when oxidised in a CCl4 suspension.The syntheses of mer-X, mer-X (X = Cl or Br), Y2, Cl2, Y2, and 2)Cl2>Cl2 (Y = Cl or ClO4) are described.Complexes were characterised by i.r., electronic, and 1H n.m.r. spectroscopy, and conductivity measurements.
