Showing papers in "Transition Metal Chemistry in 1975"
TL;DR: In this paper, the preparation and thermal decomposition of the platinum halides PtXn (X = 1, Br, Cl) have been investigated and three modifications of Ptl4 have been presented.
Abstract: The preparations and thermal decompositions of platinum halides PtXn (X = 1, Br, Cl) have been reinvestigated. The tetrahalides consist characteristically of PtX6 octahedra linked into chains by two common edges, a structural group ing present in two of three modifications of PtI4 and in PtBr4 and PtCl4. Normal thermal decomposition of PtX4 does not give the PtX3 compounds, but these can be prepared by other methods. They are all diamagnetic and for X = Cl and Br consist of both Pt(II) and PC(IV) structural elements. All three Ptl4 modifications and PtI3 decompose to a new Pt3I8 phase and subsequently to PtI2 which is dimorphic. PtBr4, PtCl4, PtBr3 and PtCl3 decompose to the respective dihalides for which there is also evidence of polymorphism.
23 citations
TL;DR: The spontaneous decomposition of the compounds MoOF2(S2CNR2)2, where R = Et or n-Pr yields salts containing the new cation [MoO(S 2CNR 2)3]- and the dimeric anion [Mo2O4F6]2− The structure of the ethyl derivative has been determined by x-ray diffraction techniques as discussed by the authors.
Abstract: The spontaneous decomposition of the compounds MoOF2(S2CNR2)2, where R = Et or n-Pr yields salts containing the new cation [MoO(S2CNR2)3]+ and the dimeric anion [Mo2O4F6]2− The structure of the ethyl derivative has been determined by x-ray diffraction techniques. It crystallizes in space group C2/c with a = 27.3 56(4) A, b = 17.292(3) A, c = 12.716(3) A,β = 103.76(3)°. All atoms, including the thirty hydrogen atoms, were used in a least-squares procedure with convergence to a conventional R factor of 0.045. The i.r. and far i.r. spectra are discussed.
22 citations
20 citations
TL;DR: In this article, a five membered metallocycle was constructed by the reaction of palladium(II) chloride with Hphpz and Htlpz in methanol in the presence of lithium chloride.
Abstract: When platinum(II) chloride dissolved in acetic acid containing concentrated hydrochloric acid was refluxed withN-phenylpyrazole(liphpz) andN-(p-tolyl)pyrazole (Htlpz), complexes of composition [Pt(N-C)Cl]2 (N-C = phpz, tlpz) were obtained, in which phpz and tlpz are coordinated through nitrogen and carbon forming a five membered metallocycle. Similar palladium(II) complexes [Pd(N-C)Cl]2 were easily prepared by the reaction of palladium(II) chloride with Hphpz and Htlpz in methanol in the presence of lithium chloride. These [M(N-C)CI]2 complexes reacted with tri-n-butylphosphine (PBu3) and pyridine (py) to give the adducts [M(N-C)ClL](L = PBu3, py). Ethylenediamine(en) and acetylacetone(Hacac) gave IPd(phpz)(en)]Cl and [Pd(phpz)(acac)] respectively. These new complexes are characterized by means of1H-n.m.r. and i.r. spectra, and probable structures are proposed.
15 citations
TL;DR: In this paper, the mechanism of the electrochemical reduction of (chromium tricarbonyl)-pivalophenone, -benzophenone and -fluorenone was studied by means of polarography and electron spin resonance spectroscopy.
Abstract: The mechanism of the electrochemical reduction of (chromium tricarbonyl)-pivalophenone, -benzophenone, and -fluorenone was studied by means of polarography and electron spin resonance spectroscopy. The polarograms of the complexed ketones in anhydrous dimethylformamide consisted of two well-defined waves: the compounds are reduced to the corresponding radical anions which are further reduced to the dinegative anion. The influence of the Cr(CO)3 group on the half-wave potentials of the first and second wave is discussed.
13 citations
TL;DR: In this paper, the reactions and properties of 2-aminothiophenol complexes of copper have been investigated under differing conditions, and it is suggested that the ligand stabilises the cupric and cuprous states to the same extent; some of the properties of its copper complexes are thereby understood.
Abstract: The reactions and properties of 2-aminothiophenol complexes of copper have been investigated under differing conditions. Inconsistencies among earlier reports arise from previously unrealised effects of atmospheric conditions and counter ion. It is suggested that the ligand is unusual in the sense that it stabilises the cupric and cuprous states to the same extent; some of the properties of its copper complexes are thereby understood. Three ligands similar to 2-amino-thiophenol have been studied. Spectral and magnetic measurements are presented; attention is drawn to unexpected results, especially in the d-d region of electronic spectra.
11 citations
TL;DR: In this article, a mixture of two phenyldiazo-rhenium complexes, [ReCl2(2Ph)(NH3)(PMe2Ph)2] and [Recl2(N2p-tolyl) (PMe 2Ph)3], were synthesized and the ammine is reversibly protonated by HCl or HBr.
Abstract: mer-[ReCl3(PMe2Pha)3] reacts with phenylhydrazine to give a mixture of two phenyldiazo-rhenium complexes, [ReCl2(2Ph)(NH3)(PMe2Ph)2] and [ReCl2(N2Ph)(PMe2Ph) The ammonia ligand is readily displaced by CO, PMe2Ph) or PEt2Ph (Q) to give [ReCl2(N2Ph)Q(PMe2Ph)2] but is not displaced by CH3CN, pyridine, CH3NC or PPh3. [ReCl2(N2p-tolyl)(PMe2Ph)3], and [ReX2(N2Ph)(PMe2Ph)2] (X = Br of I) were also synthesized. The ammine is reversibly protonated by HCl or HBr to give the slats [ReCl2(N:NlPh)NH3)(PMe2Ph)2]X, I.r and1H n. m.r. data are given and discussed.
10 citations
TL;DR: In this paper, a dinuclear anionic complex (M2X4(SO2OR)2− (1) (R = Me, Et, n-Pr).
Abstract: Platinum and palladium chloride and bromide suspended in alcohols react with sulfur dioxide to give a “MX2-SO2 -ROW” solution, containing dinuclear anionic complexes [M2X4(SO2OR)2]2− (1) (R = Me, Et, n-Pr). These complexes react variously with neutral ligands (L) depending on the metal, the ligand, and the experimental conditions.
10 citations
TL;DR: In this paper, six new compounds of the type [Mn2(O)2(A-A)4]-ClO4)3 ·2 H2O and [mn2O]2A4]-S2O8)1,5 nH2O were obtained by oxidising aqueous manganese(11) sulphate solutions in the presence of the chelate ligand.
Abstract: Six new compounds of the type [Mn2(O)2(A-A)4](ClO4)3 ·2 H2O and [Mn2(O)2(A-A)4](S2O8)1,5 — nH2O where (A-A) = 1,10-phenanthroline, 1,10-phenanthrolineN-oxide or 2,2′-bipyridine N-oxide, and n = 2 or 3, have been prepared by oxidising aqueous manganese(11) sulphate solutions in the presence of the chelate ligand (A-A).
10 citations
TL;DR: An x-ray structural analysis of the title complex (Ph4As) has been carried out in this article, where the crystals are tetragonal with unit-cell dimensions a = 13.05 3(2),c = 8.3 37(2) A, space groupP4/n and Z = 2.040.
Abstract: An x-ray structural analysis of the title complex, (Ph4As)[OsNl4], has been carried out. The crystals are tetragonal with unit-cell dimensions a = 13.05 3(2),c = 8.3 37(2) A, space groupP4/n and Z = 2. Least-squares refinement, using 1350 independent reflections measured on a diffractometer, has reachedR = 0.040.
9 citations
TL;DR: The silylacetyl derivatives desilylate when treated with traces of acid as discussed by the authors, leading to the formation of asymmetric monocarbonyl derivatives containing either a sily lacetyl ligand.
Abstract: The complex [η5-C5H5Fe(CO)2]− Na+ reacts with variously substituted silylmethyl halides to yield the corresponding new silylmethyliron complexes which react with tertiary phosphines to yield asymmetric monocarbonyl derivatives containing either a silylmethyl or silylacetyl ligand. The silylacetyl derivatives desilylate when treated with traces of acid. Sulphur dioxide inserts into the iron carbon bond to form silylmethylsulphinato complexes.
TL;DR: Transfer reactions of methyl and other metal a-bonded groups from a series of cobalt organometallic chelates (in cluding methylcobalamin) to mercury and vice-versa, are reported in this article.
Abstract: Transfer reactions of methyl and other metal a-bonded groups from a series of cobalt organometallic chelates (in cluding methylcobalamin) to mercury andvice-versa, are reported. The thermodynamically favoured reactions, valid also for the vitamin B12, are: the transfer of the methyl group as a carbanion from cobalt to mercuric (synthesis of [MeHg]+ and Me2Hg) or to mercurous ion (synthesis of [MeHg]+ + Hg(O)) and its transfer as a carbonium ion from [MeHgj+ to Co(l).