13869-38-0Relevant articles and documents
Transmetallation of Bis(6-diphenylphosphinoacenaphth-5-yl)-Mercury and -Tributyltin with Precious Metal Chlorides
Furan, Sinas,Lork, Enno,Mebs, Stefan,Hupf, Emanuel,Beckmann, Jens
, p. 856 - 865 (2020)
The reaction of bis(6-diphenylphosphinoacenapht-5yl)mercury, (6-Ph2P-Ace-5-)2Hg, with [(CO)2RhCl]2 and PtCl2 proceeded with extrusion of mercury / mercury(I) chloride and provided the octahedral rhodium and platinum complexes (6-Ph2P-Ace-5-)2Rh(CO)Cl and (6-Ph2P-Ace-5-)2PtCl2, respectively. The reaction of the (6-diphenylphosphinoacenapht-5yl)stannane 6-Ph2P-Ace-5-SnBu3 with PdCl2 gave rise to tributyltin chloride and a dimeric arylpalladium chloride [(6-Ph2P-Ace-5-)PdCl]2 with a planar Pd2Cl2 core. Together with the previously known gold(III) complex cis- and trans-[R2Au][Cl], the newly prepared compounds were investigated by DFT calculations. The fully optimized gas-phase structure of [(6-Ph2P-Ace-5-)PdCl]2 gives rise to a bend Pd2Cl2 core featuring a Pd···Pd palladophilic interaction. The bonding situation was studied using a set of real-space bonding indicators (RSBIs) derived from the methods Atoms-In-Molecules (AIM), Electron Localizability Indicator (ELI-D) and Non-Covalent Interaction (NCI) index.
Reaction of platinum complexes with (+)-α-pinene and (+)-limonene. Synthesis, molecular structure, and catalytic activity of dichloro(η 4-[p-mentha-1,8{9}-diene])platinum(II)
De Vekki,Uvarov,Bel'skii,Skvortsov
, p. 1288 - 1294 (2006)
The transformations of platinum(II) and platinum(IV) complexes with inner-and outer-sphere ligands by the action of (+)-α-pinene and (+)-limonene were studied. Reduction of the metal complex is the main process whose rate increases in the following outer-sphere ligand series: (Me 2SO)2H+ 3NH+ - +. The reaction of K2PtCl4 with α-pinene gave cis-terpine monohydrate and dichloro-η4- [p-mentha-1,8(9)-diene]platinum(II), and their structure was proved by X-ray analysis. The complex belongs to monoclinic crystal system, the Pt-Cl and Pt-C bonds therein have different lengths, the ClPtCl angle is 85.88°, and the C=C bond plane is orthogonal to the square coordination core. Dichloro-η4-[p-mentha-1,8(9)-diene]-platinum(II) was tested as catalyst in the hydrosilylation of acetophenone with diphenylsilane. Nauka/Interperiodica 2006.
An electroactive porous network from covalent metal-dithiolene links
Cui, Jieshun,Xu, Zhengtao
, p. 3986 - 3988 (2014)
Simple synthesis and versatile functions: by directly reacting a triphenylene hexathiol molecule (HTT) with PtCl2, a covalent metal-organic framework (CMOF) has been prepared that features substantial porosity, redox activity and ion exchange capability.
Catalytic cyclization of o-alkynylbenzaldehyde acetals and thioacetals. Unprecedented activation of the platinum catalyst by olefins. Scope and mechanism of the reaction
Nakamura, Itaru,Bajracharya, Gan B.,Wu, Huanyou,Oishi, Kengo,Mizushima, Yuya,Gridnev, Ilya D.,Yamamoto, Yoshinori
, p. 15423 - 15430 (2004)
A general protocol for the synthesis of functionalized indenes from o-alkynylbenzaldehyde acetals and thioacetals has been elaborated. Acetals uniformly give cyclization products having the alkyl group from the starting acetylene migrated to the α-position, whereas the cyclization of the corresponding thioacetals proceeds without alkyl migration. Optimization of the catalytic system for the cyclization of o-alkynylbenzaldehyde acetals revealed an unknown activation effect: PtCl2 was found to be a better catalyst for the cyclization of acetals in the presence of olefins than without. A similar catalytic system (PtCl2/ benzoquinone) has been found to be appropriate for the cyclization of cyclic acetals, whereas the optimal catalyst for the reaction of thioacetals is PdI2. NMR monitoring of two reactions, acetal 3a + Pd(CH3CN)-Cl2 in CD3CN and thioacetal 5j + PdI2 in CD2Cl2, revealed that in both reactions similar cationic species are formed at the early stage of the transformation. Computational data (B3LYP/SDD level of theory) suggest that the difference in the reaction pathways for acetals and thioacetals can be rationalized by taking into account the relative stabilities of the corresponding vinylpalladium intermediates (22 vs 20 and 19 vs 21), which suggests a reversible thermodynamically controlled alkyl migration in the intermediate vinylcationic species.
Complexes of Platinum Group Metals with a Conformationally Locked Scorpionate in a Metal-Organic Framework: An Unusually Close Apical Interaction of Palladium(II)
Payne, Michael T.,Neumann, Constanze N.,Stavitski, Eli,Dincǎ, Mircea
, p. 11764 - 11774 (2021/07/31)
We report synthetic strategies for installing platinum group metals (PGMs: Pd, Rh, Ir, and Pt) on a scorpionate-derived linker (TpmC*) within a metal-organic framework (MOF), both by room-temperature postsynthetic metalation and by direct solvothermal synthesis, with a wide range of metal loadings relevant for fundamental studies and catalysis. In-depth studies for the palladium adduct Pd(II)@Zr-TpmC? by density-functional-theory-assisted extended X-ray absorption fine structure spectroscopy reveals that the rigid MOF lattice enforces a close Pd(II)-Napical interaction between the bidentate palladium complex and the third uncoordinated pyrazole arm of the TpmC? ligand (Pd-Napical = 2.501 ± 0.067 ?), an interaction that is wholly avoided in molecular palladium scorpionates.
Pt(II) and Pd(II)-assisted coupling of nitriles and 1,3-diiminoisoindoline: Synthesis and luminescence properties of (1,3,5,7,9-pentaazanona-1,3,6,8-tetraenato)Pt(II) and Pd(II) complexes
Lasri, Jamal,Pedras, Bruno,Haukka, Matti,Berberan-Santos, Mário N.
, p. 195 - 202 (2017/06/13)
Treatment of trans-[PtCl2(NCR)2] 1 (R?=?Me (1a), Et (1b), o-ClC6H4 (1c), p-ClC6H4 (1d), p-(HC[dbnd]O)C6H4 (1e), p-O2NC6H4CH2 (1f)) with 1,3-diiminoisoindoline HN[dbnd]CC6H4C(NH)[dbnd]NH 2 gives access to the corresponding (1,3,5,7,9-pentaazanona-1,3,6,8-tetraenato)Pt(II) complexes [PtCl{NH[dbnd]C(R)N[dbnd]C(C6H4)NC[dbnd]NC(R)[dbnd]NH}] 3a–f, in good yields (65–70%). The reaction of trans-[PdCl2(NCMe)2] 4a with 2 furnishes (1,3,5,7,9-pentaazanona-1,3,6,8-tetraenato)Pd(II) complex [PdCl{NH[dbnd]C(Me)N[dbnd]C(C6H4)NC[dbnd]NC(Me)[dbnd]NH}] 5a, in good yield (65%). However, the reaction of trans-[PdCl2(NCR)2] 4 (R?=?Ph (4b), p-MeC6H4CH2 (4c), p-(HC[dbnd]O)C6H4 (4d), p-O2NC6H4CH2 (4e)) with 2 gives a number of unidentified products. The compounds 3a–f and 5a were characterized by IR,1H,13C and DEPT-135 NMR spectroscopies, elemental analyses and, in the case of the Pt(II) complex [PtCl{NH[dbnd]C(Me)N[dbnd]C(C6H4)NC[dbnd]NC(Me)[dbnd]NH}] 3a, also by X-ray diffraction analysis. Compounds 3a and 3b were also characterized by UV–Vis absorption and luminescence emission spectroscopies. Emission quantum yields of ca. 3?×?10?3 were obtained in dichloromethane solution, and luminescence lifetimes are in the order of the tens of nanoseconds. Both compounds also exhibited luminescence in solid state (polystyrene matrix), with luminescence lifetimes in the order of hundreds of nanoseconds.
PHOSPHINE COMPOUND HAVING PERFLUORO GROUP, AND COMPLEX BETWEEN METAL AND PHOSPHINE HAVING PERFLUORO GROUP
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Paragraph 0252-0254, (2018/10/16)
PROBLEM TO BE SOLVED: To provide a perfluoroalkylphosphine compound, and a complex between a metal and the perfluoroalkylphosphine. SOLUTION: A perfluoroalkylphosphine compound is a phosphine compound represented by the general formula Rf-PR1R2. In the formula, R1 and R2 are each independently a substituted or unsubstituted hydrocarbon group; Rf is a perfluorinated hydrocarbon group. Also provided is a complex between the perfluoroalkylphosphine and a phosphine coordination metal. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
METHODS OF PRODUCING PHOSPHINE COMPOUND HAVING PERFLUORO GROUP AND COMPLEX BETWEEN METAL AND PHOSPHINE HAVING PERFLUORO GROUP
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Paragraph 0217-0218, (2018/10/19)
PROBLEM TO BE SOLVED: To provide methods of producing a perfluoroalkylphosphine compound improved in a phosphorus element yield and a chemical yield. SOLUTION: A method of producing a perfluoroalkylphosphine compound comprises either reacting a perfluoroalkyl iodide with, e.g., 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TMDPO) or a triarylphosphine such as triphenylphosphine, which are easily available, in the presence of a radical generator such as azobis(isobutyronitrile) or light irradiation, or reacting TMDPO or the like with perfluoroalkyl iodide in the presence of diphenylphosphine, diethylphosphine, dicyclohexylphosphine or the like. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
Two-photon-activated ligand exchange in platinum(II) complexes
Zhao, Yao,Roberts, Gareth M.,Greenough, Simon E.,Farrer, Nicola J.,Paterson, Martin J.,Powell, William H.,Stavros, Vasilios G.,Sadler, Peter J.
supporting information, p. 11263 - 11266 (2013/01/15)
Two photons are better than one: A square-planar PtII complex with derivatized pyridine ligands was synthesized (see scheme), which undergoes two-photon-induced ligand substitution with 600-740 nm light. Linear and quadratic density functional response theory allowed identification of the electronic transitions involved. Copyright
Synthesis, structures, and electronic spectroscopy of luminescent acetylene- and (buta-1,3-diyne)platinum complexes
Zhang, Ke,Hu, Jian,Kwok, Chu Chan,Kwok, Yin Wong,Yip, John H. K.
, p. 384 - 393 (2007/10/03)
The electronic absorption and emission spectroscopy of a series of diphenylaceylene- and (buta-1,3-diyne)-Pt0 complexes (L)Pt[(1,2-η2)-R-(C≡C)n-R] and [(dppp)Pt] 2[μ-(1,2-η2):(3,4-η2)-R-(C≡C) 2-R] (R = Ph or CH3, L = dppp or (PPh3) 2, n = 1 or 2) was investigated. The structures of (dppp)Pt[(1,2-η2)-Ph-C≡C-Ph], (dppp)Pt[(1,2- η2)-PhC4Ph] and [(dppp)Pt]2[μ-(1,2- η2):(3,4-η2)-Ph-(C≡C)2-Ph] were characterized by X-ray diffraction. The complexes all display intense absorptions that were attributed to Pt→P(dπ*) and Pt→acetylene(πx*) transitions. Except for the CH 3C4CH3 complexes, the complexes all exhibit two emissions at 380-550 nm and 500-800 nm. The higher energy emission could arise from the 3[P(dπ*)→Pt] transition, and the lower energy emission, which has a longer lifetime than the higher energy one, was attributed to the 3[acetylene(πx*)→Pt] transition. The energy of the MLCT absorption and emission was affected by the electronic properties of the acetylenes and the ancillary phosphanes. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
