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  • 1
    ISSN: 0009-2940
    Keywords: Ruthenium complexes ; Osmium complexes ; Insertion reactions ; Carbon disulfide ; Carbon dioxide ; Methyl isothiocyanate ; Zwitterionic ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The five-coordinate chloro(hydrido)- and hydrido(iodo)ruthenium(II) and -osmium(II) compounds [MHX(CO)(PiPr3)2] (1, 2, 6, 7) react with CS2 to give the octahedral dithioformato complexes [MCl(CO)(PiPr3)2(η2-S2CH)] (3, 4, 8, 9) in excellent yields. In the initial step, an addition of the heteroallene to the metal center occurs which is followed by insertion of CS2 into the M - H bond. On treatment of the dichlororuthenium(II) derivative [RuCl2(CO)(PiPr3)2] (10), which is prepared from RuCl3 · aq and PiPr3 in methanol, with carbon disulfide insertion into one of the Ru - PiPr3 bonds takes place to give the six-coordinate ruthenium(II) complex 12 with zwitterion -S2CPiPr3+ as a chelating ligand. While the reaction of [OsH(SPh)(CO)(PiPr3)2] (13) with MeSCN leads to addition of the thionitrile to the metal center, the starting material reacts with MeNCS by insertion of the heteroallene into the Os - SPh bond to give two stereoisomers 15a, b, in which the nitrogen atom of the chelate ring is either cis or trans to the hydrido ligand. The octahedral methoxydithiocarbonato- and formatoosmium(II) compounds 16 and 17 are prepared from 2 and CS2 or CO2 in the presence of NaOMe. The crystal and molecular structures of 4 (M = Os), 12 and 15a have been determined.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0009-2940
    Keywords: Arsane, triisopropyl, rhodium complexes of ; Stibane, triisopropyl, rhodium complexes of ; Rhodium(I) complexes, square-planar, with carbonyl, ethylene, alkyne, and vinylidene ; Rhodium(III) compounds [RhH2Cl(EiPr3)2] (E=As, Sb), five-coordinate, dihydrido- ; Allenerhodium complexes, generation from alkynes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of the dimeric bis(olefin)rhodium(I) compounds [RhCl(olefin)2]2 [olefin=C8H14 (2), C2H4 (5)] with AsiPr3 and SbiPr3 gives mono- and dinuclear olefin(arsane) and olefin(stibane) complexes [RhCl(olefin)(EiPr3)]2 [olefin=C8H14 (3, 4), C2H4 (6, 7)] and trans-[RhCl(C2H4)(EiPr3)2] (8, 9). Treatment of 8 and 9 with CO, H2, and CPh2N2 leads to the displacement of the ethylene ligand with formation of the corresponding carbonyl (10, 11), dihydrido (12, 13), and diazoalkane (14) rhodium derivatives. In solution, compound 14 loses CPh2 to give trans-[RhCl(N2)(AsiPr3)2] (15). The alkyne complexes trans-[RhCl(HC≡C̊)(AsiPr3)2] (16-18), which are prepared either from 8 or [RhH2Cl(AsiPr3)2] (12) and HC≡C̊ (R=H, Ph, CO2Me), rearrange in solution to produce the vinylidenerhodium isomers trans-[RhCl(=C=CHR)(AsiPr3)2] (19-21). Reaction of 8 with HC≡CMe and HC≡CtBu leads directly to the vinylidene complexes 22, 23. Compound 8 reacts with excess propyne, but-2-yne, or 2,2-dimethylpent-2-yne to give the rhodium allenes trans-[RhCl(η2-CH2=C=CHR)(AsiPr3)2] (25-27) in nearly quantitative yields. With DC≡CMe as a substrate, it is shown that two propyne molecules are involved in the rearrangement to generate the coordinated allene. The crystal and molecular structure of trans-[RhCl(η2-CH2=C=CH2)(AsiPr3)2] (27) has been determined.
    Additional Material: 1 Ill.
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  • 3
    ISSN: 0009-2940
    Keywords: Osmium complexes ; Hydrido complexes ; Functionalized phosphane ligands ; Phosphanylmethanide ligand ; Phosphanyl alcoholate ligand ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mononuclear dichloroosmium(II) complexes [(mes)-Os(L)Cl2] (2-5) with the phosphanyl ether L = iPr2PCH2-CH2OMe and phosphanyl esters L = IPr2P(CH2)nCO2R as ligands are obtained from [(mes)OsCl2]n and L in almost quantitative yield. While compound 3 (L = iPr2PCH2CH2CO2Me) reacts with Mg/Hg in THF in the presence of ethanol to give the monohydrido derivative 6, treatment of 4 (L = iPr2PCH2-CO2Me) or 5 (L = iPr2PCH2CO2Et) with Al2O3/NaH in THF yields the phosphanylmethanide complexes [(mes)-Os{k2(P,C)-iPr2PCHCO2R}Cl] (7, 8). In contrast to the reaction of 4 with Mg/Hg in THF/EtOH which yields the dihydrido compound [(mes)OsH2{k(P)-iPr2PCH2CO2Me}] (10), the corresponding reaction of 4 with excess PhMgBr does not lead to an OsPh2 species but instead gives the new chelate complex [(mes)OsPh{k2(P,O)-iPr2PCH2CPh2O}] (11). The crystal and molecular structures of 7 and 11 were determined.
    Additional Material: 2 Ill.
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  • 4
    ISSN: 0009-2940
    Keywords: Cationic amido osmium(II) complexes, synthesis from dichloro metal precursor and primary amines ; Os-N double bond ; Aldimino(hydrido)osmium(II) complex, formation by β1-hydride migration ; Amino(chloro)osmium(II) complex, preparation by protonation of an amido derivate ; Dinuclear imidoosmium complex, presence of a Os2N2 four-membered ring ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbene-Type Amidoosmium Complexes with an Os—N Double Bond: Synthesis, Structure and Reactivity of [(Mes)Os(=NHR)(PiPr3)]PF6*The reaction of [(Mes)Os(PiPr3)Cl2] (1) (Mes=1,3,5-C6H3Me3) with primary amines RNH2 (R=Ph, Me, Et) in acetone/water (1:1) gives, after addition of KPF6, the amidoosmium(II) complexes [(Mes)Os(=NHR)(PiPr3)]PF6 (2-4) in 60-80% yield. From 1 and Et2NH, the chloro(hydrido)compound [(Mes)1-OsH(PiPr3)Cl] (5) is formed. The X-ray structural analysis of 2 reveals that the geometry around the osmium atom is trigonalplanar (with the midpoint of the mesitylene ring as one coordination site) and that the Os—N distance of 1.923(4) Å is in agreement with an Os—N double bond. Thermolysis of 4 (R=Et) at 165°C leads to the formation of the aldimino(hydrido)osmium complex [(Mes)OsH(NH=CHMe)(PiPr3)]PF6 (6) by β1-hydride migration from the NCH2 carbon atom to the metal atom. Protonation of 3 (R=Me) with HCl gives the amine complex [(Mes)Os(NH2Me)(PiPr3)Cl]PF6 (7), whereas on treatment of 3 and 4 with CD3NO2 the deuterated derivatives [(Mes)Os(=NDR)(PiPr3)]PF6 ([D1]-3, [D1]-4) are almost quantitatively formed. Compound 2 (R=Ph) reacts with KOtBu by proton abstraction and phosphane elimination to give the dinuclear imidoosmium complex [(Mes)2Os2(μ1-NPh)2] (8).
    Additional Material: 2 Ill.
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  • 5
    ISSN: 0009-2940
    Keywords: Alkynes, (triphenylstannyl)- ; Rhodium(I) complexes, vinylidene ; Rhodium(III) complexes, alkynyl(hydrido)-and bis(alkynyl)hydrido- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of [RhCl(PiPr3)2]n (1) with stannylalkynes RC≡CSnPh3 [R = H, Me, Ph, CH2OH, CH2OMe, CMe2OH, CH(Me)OH, CH(Ph)OH, SiMe3, SnPh3] gives the vinylidenerhodium(I) complexes trans-[RhCl(=C=C(SnPh3)R)(PiPr3)2] (2a-j) in good to excellent yields. These compounds react with protic acids to give trans-[RhCl(=C=CHR)(PiPr3)2] and, for R = CH(Ph)OH, to give the allenylidene complex trans-[RhCl(=C=C=CHPh)-(PiPr3)2] (5). On treatment of 2b-j with PhHgCl, the heterodimetallic compounds [Rh(C≡C̊)(HgPh)Cl(PiPr3)2] (6a-i) are formed. The bis(alkynyl)rhodium(III) complexes [RhH(C≡CSi-Me3)(C≡CSnPh3)(py)(PiPr3)2] (9) and [Rh(C≡CSiMe3)(C≡C—CH2OMe)(SnPh3)(PiPr3)2] (10) are prepared from trans-[Rh-(C≡CSiMe3)(L)(PiPr3)2] (7, 8, L = py, C2H4) and HC≡CSnPh3 or Ph3SnC≡CCH2OMe, respectively. The crystal and molecular structures of trans-[RhCl(=C=C(SnPh3)CH2OMe)(PiPr3)2] (2e) and [Rh(C≡CCH2OMe)(HgPh)Cl(PiPr3)2] (6d) have been determined.
    Additional Material: 2 Ill.
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