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.
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.
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.
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
