On the Mechanism of the Thermal Decomposition of Ammonium and Ammin Chloro Complexes of Ruthenium, Rhodium, Palladium and Platinum The thermolysis of noble metal compounds was investigated by a combination of independent physical (DTA/TG, high-temperature Guinier-Simon-technique) and preparative methods, characterization of the educts, intermediats and products by Guinier X-ray patterns and IR spectroscopy:
(a) (NH4)2[PtCl6], (NH4)2[PtCl4], [Pt(NH3)4][PtCl4], [Pt(NH3)4]Cl2, and trans-[Pt(NH3)2Cl2];
(b) (NH4)2[PdCl4], [Pd(NH3)4]Cl2, trans-[Pd(NH3)2Cl2], and [Pd(NH3)4][PdCl4];
(c) (NH4)2[RhCl5(H2O)], (NH4)3[Rh2Cl9], K2[RhCl5(H2O)], and K2[RhCl5(NH3)];
(d) (NH4)2[RuCl5(NH3)] and (NH4)4[Ru2Cl10O]
. The most important step of the mechanism of the thermal decomposition is the ?internal”? redox reaction between the noble metal cation and the nitrogen atom of the ammine ligand. 相似文献
New 1,1′-Ferrocene Dichalcogenato Complexes of Ruthenium and Osmium Both trinuclear 1,1′-ferrocene dichalcogenato complexes(1) such as fc(E[MLn])2 ( 1a—c ) (with [MLn] = Ru(CO)2Cp*; E = S, Se, Te) and dinuclear [3]ferrocenophane derivatives of the type fcE2[MLn] (with [MLn] = Ru(CO)(η6-C6Me6) ( 2a, b ), Ru(NO)Cp* ( 3a, b ) (E = S, Se) or Os(NO)Cp* ( 4a—c ) (E = S, Se, Te)) were synthesized and characterized by their IR-, 1H- and 13C NMR spectra as well as their mass spectra. The molecular structure of fcS2[Os(NO)Cp*] ( 4a ) was determined by an X-Ray structure analysis; the long Fe…?Os distance of 431.1(1)pm excludes any direct bonding interactions. 相似文献
Preparation and Properties of New Cationic Dienyl-isonitrile-dicarbonyl Complexes of Iron and Ruthenium The hydride abstraction from the η4-diene isonitrile metal dicarbonyls M(η4-dien)(CNR)(CO)2 (M = Fe, Ru; dien = C6H8 cyclohexadiene-1.3; C7H10 cycloheptadiene-1.3; R = Me, Et) with [Ph3C]BF4 lead to the η5-dienyl isonitrile dicarbonyl metal cations [M(η5-dienyl)(CNR)(CO)2]+ [dienyl = cyclohexa-2.4-dien-1-yl (C6H7), cyclohepta-2.4-dien-1-yl (C7H9)]. [Fe(η5? C8H9)(CNMe)(CO)2]+ (C8H9 = bicyclo[5.1.0]octa-3.5-dien-2-yl) is formed by protonation of Fe(η4? C8H8)(CNMe)(CO)2 (C8H8 = COT) under valency isomerization. The two cations [Fe(η5? C7H9)(CNMe)(CO)2]+ and [Fe(η5? C8H9)(CNMe)(CO)2]+ can be deprotonated with NEt3 to the neutral cycloheptatriene respectively COT complexes Fe(η4? C7H8)(CNMe)(CO)2 and Fe(η4? C8H8)(CNMe)(CO)2. The temperature dependent 13C-NMR spectra of [Fe(η5? C7H9)(CNMe)(CO)2]+ and [Ru(η5? C6H7)(CNMe)(CO)2]+ show the fluctional behaviour of these cations in solution. At low temperatures one CO group occupies the apical position of a square pyramid whereas the isonitrile ligand, the other CO group and the dienyl part are in the basal positions. The ΔG values of the CP exchange points out a higher activation energy as in the corresponding η4-diene metal complexes. 相似文献
Synthesis, Characterization, and Structure of Carbonyl and Hydrido Isocyanato Complexes of Ruthenium [Ru(CO)H(NCO)(PPh2Me)3] is formed during the reaction between [RuCl3(PPh2Me)3] and NaOCN in EtOH. The compound crystallizes in the monoclinic space group P21/n (a = 1256.4(4), b = 1487.2(2), c = 1993.5(5) pm, β = 97.28(1)°, Z = 4). The distorted octahedral coordination sphere of RuII contains the phosphine ligands in meridional arrangement, their P atoms forming a plane together with the hydride ligand. The reaction of [RuCl3(PPh3)2] with NaOCN in EtOH yields [Ru(NCO)(CO)(CH3COO)(PPh3)2] with trans coordinated Ph3P ligands. The formation of hydrido, carbonyl and acetato ligands are due to the reaction of the transition metal with the solvent ethanol. 相似文献
Chemistry of Polyfunctional Molecules. 118. Syntheses and Crystal Structures of Bicyclic Metallaphosphazenes with Four and Six Membered Rings Anhydrous MCl2 (M = Pt, Fe) react with LiN(PPh2)2 ( 1 ) in the molar ratio of 1:2 in boiling toluene within 25 hours under partially oxidative scrambling of the PNP chain in 1 yielding the bicyclic metallaphosphazenes 5 a, b . While compound 5 a can be isolated in substance, the intermediate 5 b proves to be highly reactive but can be stabilized in the presence of CO, forming the 18-valence-electron coordination compound as an isomeric trans( 6 a )/cis( 6 b ) mixture in the molar ratio of 99:1. Also treatment of anhydrous PtCl4 with four equivalents of 1 in boiling toluene during 60 hours yields 5 a . Alkylation of 5 a with CH3I leads to the formation of the ionic species [Pt2+{Ph2P? N(CH3)? PPh2}(Ph2P? N = PPh2 = N? PPh2?)]I? ( 9 ). The X-ray crystal structures of 5 a × 1 CH2Cl2 and 6 a reveal, that the metal centres have a planar P-coordination polyhedron in the solid state. In the complex 9 × 2,5 CH2Cl2 however the torsion angle between the P? Pt? P planes of the four and six membered rings shows to be 15°. The six membered metallacycles in 5 a × 1 CH2Cl2, 6 a and 9 × 2,5 CH2Cl2 differ in their geometrical arrangement. All the new compounds have also been characterized by their 1H, 31P{1H}, 13C{1H} NMR, IR, Raman and mass spectra. 相似文献
Zusammenfassung Osmiumhalogenidlösungen bilden mit Phosphonium- und Arsoniumsalzen schwerlösliche Niederschläge. Nach Ermittlung der Löslichkeiten dieser Niederschläge in Abhängigkeit von der Reagens- und Säurekonzentration können die Gebiete einer quantitativen Ausfällung des Osmiums angegeben werden. Die zur Auswaage notwendige Reinheit und stöchiometrische Zusammensetzung der Fällungen wird allerdings nur unter Einhaltung bestimmter Arbeitsvorschriften bei einigen Reagentien erreicht.Für die Bestimmung des Osmiums in salzsaurer Lösung werden empfohlen: Tetraphenylarsoniumchlorid und Benzyltriphenylphosphoniumchlorid. In bromwasserstoffsaurer Lösung sind geeignet: Tetraphenylarsoniumchlorid und Tetraphenylphosphoniumsalz.VII. Mitteilung: Neeb, R.: diese Z. 159, 401 (1957/58).Herrn Prof. Dr. W. Geilmann danke ich für anregende Diskussionen zum Thema, Herrn Prof. Dr. F. Strassmann für die Bereitstellung von radioaktivem Ruthenium und Herrn Prof. Dr. L. Horner für zahlreiche Phosphoniumsalze. 相似文献
