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  • Inorganic Chemistry  (103)
  • Hydrido complexes  (9)
  • Rhodium complexes  (5)
  • 1
    ISSN: 1434-1948
    Keywords: Ruthenium ; Terminal alkynes ; Carbene complexes ; Hydrido complexes ; Vinylidene complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dichlorodihydridoruthenium(IV) compound [RuH2Cl2(PiPr3)2] (4) was prepared from [RuCl2(C8H12)]n (3), PiPr3, and H2 in 2-butanol via the chlorohydridoruthenium(II) derivative [RuHCl(H2)(PiPr3)2] (5) as an intermediate. The synthesis of 5 was achieved under similar conditions from 3, PiPr3, H2, and 2-butanol in the presence of NEt3. Compound 4, which was characterized by X-ray crystal structure analysis, reacts with excess phenylacetylene to give the phenylvinylidene complex [RuCl2(=C=CHPh)(PiPr3)2] (7) and with propargylic alcohols or derivatives thereof to afford the vinylcarbene complexes [RuCl2(=CHCH=CR2)(PiPr3)2] (9, 10), respectively. From 5 and terminal alkynes RC≡CH the chlorohydridovinylidene compounds [RuHCl(=C=CHR)(PiPr3)2] (11, 12) were obtained. The phenylvinylidene complex [RuCl2(=C=CHPh)(PCy3)2] (15) was prepared from phenylacetylene and either [RuH2Cl2(PCy3)2] (14) or one of the carbene deriva-tives [RuCl2(=CHR)(PCy3)2] (16, 17) as starting materials. The X-ray crystal structure analysis of 15 confirms a distorted square-pyramidal geometry with the vinylidene ligand in the apical position. The interconversion of 4 to 5 and of the tricyclohexylphosphane counterparts 14 to 13 was achieved by hydrogen transfer from 2-propanol in the presence of PR3. The reverse reaction occurs upon treatment of 5 or 13 with the corresponding phosphonium salt [HPR3]Cl or HCl, respectively.
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  • 2
    ISSN: 1434-1948
    Keywords: Carbene complexes ; Carbonyl complexes ; Diazoalkanes ; Hydrido complexes ; Ruthenium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The five-coordinate compound [RuHCl(CO)(PiPr2Ph)2] (1), which was prepared from RuCl3· 3 H2O and PiPr2Ph in methanol in the presence of NEt3, reacts with CO and with diazoalkanes RCHN2 (R = Ph, H) to give the six-coordinate complexes [RuHCl(CO)2(PiPr2Ph)2] (4) and [RuHCl(CO)(=CHR)(PiPr2Ph)2] (5, 6), respectively. If the reaction of 1 with CH2N2, which at -78 °C affords 6, is carried out at room temperature, the ionic compound [MePiPr2Ph][RuHCl2(CO)(PiPr2Ph)2] (7) is formed. The corresponding PPN salt was obtained from 1 and [PPN]Cl. The X-ray crystal structure analysis of 7 revealed, that the anionic species [RuHCl2(CO)(PiPr2Ph)2]- contains the chloro ligands in cis and the phosphanes in trans disposition. The Ru=CH2 bond of compound 6 is quite labile and, therefore, the CH2 unit is easily displaced by CO or pyridine. From 1 and pyridine, an isomeric mixture of [RuHCl(CO)(py)(PiPr2Ph)2] (9a, b) is formed. Treatment of 1 with HC≡CR (R = H, Ph) yields the five-coordinate vinylruthenium(II) complexes [Ru(CH=CHR)Cl(CO)(PiPr2Ph)2] (12, 13) by insertion of the alkyne into the Ru-H bond. The preparation of [RuHX(CO)-(PiPr2Ph)2] (X = CF3CO2, I) is also reported.
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  • 3
    ISSN: 1434-1948
    Keywords: Osmium ; Carbene complexes ; Hydrido complexes ; Diazoalkane complexes ; Vinyl complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The five-coordinate compound [OsHCl(CO)(PiPr3)2] (1) reacts with CH2N2 and other diazoalkanes RCHN2 (R = Ph, CO2Et, SiMe3) in ether or toluene at 25 °C to give instead of the expected insertion products [Os(CH2R)Cl(CO)(PiPr3)2] the isomeric hydrido(carbene)osmium(II) complexes [OsHCl(=CHR)(CO)(PiPr3)2] (2-5) in excellent yields. With Me3SiCHN2 as the substrate, the 1:1 adduct [OsHCl(N2CHSiMe3)(CO)(PiPr3)2] (6) was detected at low temperature as an intermediate. The reactions of 1 with Ph2CN2 and Cl4C5N2 afford the hydrido(diazoalkane)compounds [OsHCl(N2CR2)(CO)(PiPr3)2] (7, 8), which are quite stable and do not eliminate N2 to give the corresponding hydrido(carbene)metal derivatives. Treatment of 3 (R = Ph) with either HCl or HBF4/H2O leads to the cleavage of the Os-H bond and results in the formation of [OsCl2(=CHPh)(CO)(PiPr3)2] (10) and [OsCl(=CHPh)(OH2)(CO)(PiPr3)2]BF4 (11), respectively. The vinyl compound [OsCl(CH=CHPh)(CO)(PiPr3)2] (12) behaves similarly to 1 and affords the carbene complex [OsCl(CH=CHPh)(=CHPh)(CO)(PiPr3)2] (13) upon treatment with PhCHN2. Compound 13 rearranges in solution at room temperature to give the π-allyl complex [Os(η3-PhCHCHCHPh)Cl(CO)(PiPr3)2] (14) as the dominating species. The crystal and molecular structures of 4, 5, 10, and 11 have been determined by X-ray crystallography.
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  • 4
    ISSN: 1434-1948
    Keywords: Osmium ; Alkynes ; Carbyne complexes ; Hydrido complexes ; Vinylidene complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of OsCl3·2H2O with PCy3 leads under reducing conditions either to [OsH6(PCy3)2] (1) or [OsH2Cl2(PCy3)2] (2). Treatment of 2 with terminal alkynes HC≡CR (R = Ph, SiMe3) affords the carbynehydrido complexes [OsHCl2(≡CCH2R)(PCy3)2] (4, 5), of which 5 (R = SiMe3) is easily converted with traces of water into [OsHCl2(≡CCH3)(PCy3)2] (6). Compound 4 (R = Ph) reacts with NaOMe to yield the vinylidenehydridoosmium(II) complex [OsHCl(=C=CHPh)(PCy3)2] (7) which upon treatment with HBF4/OEt2 gives the five-coordinate cationic species [OsHCl(≡CCH2Ph)(PCy3)2]-BF4 (8). The reaction of [OsH3Cl(PCy3)2] (9) with HC≡CC(CH3)2Cl affords a mixture of [OsHCl2(≡CCH=CMe2)(PCy3)2] (10) and [OsCl2(H2)(=CHCH=CMe2)(PCy3)2] (11). Compound 11 is quite labile and by elimination of H2 gives 10. The molecular structure of 10 has been determined by X-ray crystallography.
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  • 5
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Basic Metals, III. Stable Cationic Hydrido-, Methyl-, and Acylcobalt ComplexesThe complexes C5H5CoL2 (L=PMe3, PMe2Ph, PMePh2) (6-8) have been prepared starting from ClCoL3 and TlC5H5. The chloro compounds ClCoL3 can be obtained by reduction of CoCl2 via CoL4 (L=PMe2Ph) or, directly, from CoCl2 and Zn in the presence of L (L=PMePh2). The reactions of 6-8 with HX and CH3 I give the cations [C5H5CoHL2]+ and [C5H5CoCH3L2]+, respectively, containing very stable Co—H and Co—CH3 bonds. The compounds [C5H5CoC2H5-(PMe3)2]I (18) and [C5H5CoC(O)R(PMe3)2]PF6 (R=CH3, C6H5) (20, 21) have also been prepared. [C5H5CoH(PMe3)2]BF4 (9) reacts at higher temperatures with excess HBF4 in propionic anhydride to form [C5H5Co(PMe3)3](BF4)2 (23). An intermediate compound [C5H5Co(PMe3)2C6H10O3]-(BF4)2 (C6H10O3=propionic anhydride) (22) has been isolated. The mechanism of this reaction is discussed.
    Notes: Die Komplexe C5H5CoL2 (L=PMe3, PMe2Ph, PMePh2) (6-8) werden ausgehend von ClCoL3 und TlC5H5 synthetisiert. Die Chloroverbindungen ClCoL3 sind durch Reduktion von CoCl2 über CoL4 (L=PMe2Ph) oder direkt aus CoCl2 und Zn in Gegenwart von L (L=PMePh2) zugänglich. Durch Reaktion von 6-8 mit HX bzw. CH3I entstehen die Kationen [C5H5CoHL2]+ bzw. [C5H5CoCH3L2]+, die sehr stabile Co—H- bzw. Co—CH3-Bindungen enthalten. Die Verbindungen [C5H5CoC2H5(PMe3)2]I (18) und [C5H5CoC(O)R(PMe3)2]PF6 (R=CH3, C6H5) (20, 21) können ebenfalls dargestellt werden. [C5H5CoH(PMe3)2]BF4 (9) reagiert bei erhöhter Temperatur mit einem Überschuß HBF4 in Propionsäure-anhydrid zu [C5H5Co(PMe3)3](BF4)2 (23), wobei als Zwischenverbindung [C5H5Co(PMe3)2C6H10O3](BF4)2 (C6H10O3=Propionsäure-anhydrid) (22) isoliert werden kann. Der Mechanismus dieser Reaktion wird diskutiert.
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  • 6
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Basic Metals, XI. Cationic (Cyclopentadienyl)rhodium Complexes Containing Rh—H-, Rh—C-, Rh—Ge-, Rh—Sn-, and Rh—Halogen Bonds[C8H12RhCl]2 reacts with excess trimethylphosphane to give [(PMe3)4Rh]Cl (1). A very rapid exchange of the phosphane ligands occurs in solution of 1. The reaction of 1 with T1C5H5 leads to the complex C5H5Rh(PMe3)2 (9), in which the metal atom is a strong Lewis base. 9 reacts very readily with electrophiles Y+ to give the cations [C5H5(PMe3)2RhY]+ which possess stable Rh—H, Rh-alkyl, Rh—acyl, Rh—Ge, Rh—Sn, and Rh—halogen bonds. They were isolated as PF6 salts [Y = H (2), CH3 (3), C2H5 (4), COCH3 (10), COC6H5 (11), COC6H4OMe-(p) (12), GeMe3 (7). SnMe3 (8). Br (15), cl (13), I (14). The cation Me3SiC5H4(PMe3)2RhH ]+ is formed together with [C5H5(PMe3)2RhH]+ in the reaction of 9 with CF3SO3SiMe3, in ether. Reduction with NaH in THF gives Me3SiC5H4Rh(PMe3)2.
    Notes: [C8H12RhCl]2 reagiert mit einem Überschuß von Trimethylphosphan zu [(PMe3)4Rh]Cl (1). In Lösungen von 1 findet ein sehr rascher Austausch der Phosphanliganden statt. Die Reaktion von 1 mit TIC5H5 führt zu dem Komplex C5H5Rh(PMe3)2 (9), der ein stark Lewis-basisches Metallatom besitzt. 9 reagiert mit Elektrophilen Y+ sehr bereitwillig zu den Kationen [C5H5(PMe3)2RhY]+ die stabile Rh—H-, Rh—Alkyl-, Rh—Acyl-, Rh—Ge-, Rh—Sn- und Rh—Halogen-Bindungen besitzen und als PF6-Salze isoliert werden [Y = H (2), CH3 (3), C2H5 (4), COCH3 (10), COC6H5 (11), COC6H4OMe-(p) (12), GeMe3 (7), SnMe3 (8), Br (15), Cl (13). 1(14)]. Bei der Reaktion von 9 mit CF3SO3SiMe3 in Ether entsteht neben [C5H5(PMe3),2RhH] + das Kation [Me3SiC5H4(PMe3)2RhH]+. Die Reduktion mit NaH in Tetrahydrofuran ergibt Me3SiC5H4Rh(PMe3)2.
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  • 7
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Basic Metals, X. C5H5Co(PMe3)2 as Building Block for the Formation of Metal-Metal BondsC5H5Co(PMe3)2 (1) reacts with equimolar amounts of ZnCl2 and PMe3 to give the complex C5H5(PMe3)2CoZnCl2(PMe3)(2). Contrary, 1, ZnCl2 and PPh3 react to give a mixture of C5H5(PMe3)2CoZnCl2 (3) and (PPh3)2ZnCl2. The reaction of 2 with PMe3 leads to cleavage of the Co—Zn bond with formation of 1 and (PMe3)2ZnCl2. - 1 reacts with [(PMe3)2CuCl]2 to give C5H5(PMe3)2CoCuCl(PMe3)2(4). In this complex and in 2, the metal atoms are probably tetrahedrally coordinated. Reaction of 4 with PMe3 leads to 1 and (PMe3)3CuCl. - Complexes having Co—Sn bonds can be synthesized through reaction of 1 with SnCl4. Me3SnCl. and Ph3SnCl. The 1:1 adducts 5, 8, and 9 that are first formed react with SnCl4 or NH4PF6 with loss of a chloride ion and formation of the cationic complexes [C5H5(PMe3)2CoSnR3]+ (R = Cl, Me, Ph) (6, 11 and 12). Electrophilic substitution of the SnMe3 group in [C5H5(PMe3)2CoSnMe3]PF6 (11) by SnCl4 or HgCl2 leads to [C5H5(PMe3)2CoSnCl3]PF6 (10) or [C5H5(PMe3)2CoHgCl]PF6 (14), respectively. - With HgCl3 1 forms both a 1:1 and a 1 :2 adduct (13 and 15). Structural suggestions for these compounds are discussed.
    Notes: C5H5Co(PMe3)2 (1) reagiert mit äquimolaren Mengen ZnCl2 und PMe3 zu dem Komplex C5H5(PMe3)2CoZnCl2(PMe3)(2). Aus 1, ZnCl2 und PPh3 entsteht dagegen ein Gemisch von C5H5 (PMe3)2CoZnCl2 (3) und (PPh3)2ZnCl2. Die Reaktion von 2 mit PMe3 führt unter Spaltung der Co—Zn-Bindung zu 1 und (PMe3)2ZnCl2. - Mit [(PMe3)2CuCl]2 reagiert 1 zu C5H5(PMe3)2CoCuCl(PMe3)2(4), in dem wahrscheinlich wie in 2 beide Metallatome tetraedrisch koordiniert sind. Bei der Umsetzung von 4 mit PMe3 bildet sich 1 und (PMe3)3CuCl. - Die Synthese von Komplexen mit Co—Sn-Bindungen gelingt durch Reaktion von 1 mit SnCl4, Me3SnCl und Ph3SnCl. Die primär gebildeten l : l-Addukte 5, 8 und 9 reagieren mit SnCl4 bzw. NH4PF6 unter Abspaltung eines Chlorid-Ions und Bildung der kationischen Komplexe [C5H5(PMe3)2CoSnR3]+(R = Cl, Me, Ph) (6, 11 und 12). Die elektrophile Substitution der SnMe3-Gruppe in [C5H5(PMe3)2CoSnMe3]PF6 (11) durch SnCl4 bzw. HgCl2 führt zu [C5H5(PMe3)2CoSnCl3]PF6 (10) bzw. [C5H5(PMe3)2CoHgCl]PF6 (14). - Mit HgCl2 bildet 1 sowohl ein 1:1- als auch ein 1:2-Addukt (13 und 15). Strukturvorschläge für diese Verbindungen werden diskutiert.
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  • 8
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Studies on the Reactivity of Metal π-Complexes, XXXI. Dinuclear Palladium(I) Complexes with Bridging Carboxylate LigandsThe reaction of [2-RC3H4Pd]2(OCOR′)2 [R = H, CH3, i-C3H7, t-C4H9 and R′ = CH3 (3), C6H5 (7), CF3 (9)] with an equimolar amount of Pd[P(i-C3H7)3]2 in hexane produces in very good yields the dinuclear complexes (2-RC3H4)(OCOR′)Pd2[P(i-C3H7)3]2 (6, 8, 10) in which palladium has the oxidation state +1. The synthesis of (C5H5)(OCOCH3)Pd2[P(i-C3H7)3]2 (15) starts with the diolefin complexes[Cl(C6H8)Pd]2(OCOCH3)2 (11) and [Cl(C7H10)Pd]2(OCOCH3)2 (12) which react with TlC5H5 to give C5H5Pd(dien)OCOCH3 [dien = 1,3-C6H8 (13), 1,3-C7H10 (14)]. The reaction of 13 or 14 with Pd[P(i-C3H7)3]2 gives 15. In the complexes 11 - 14 the diolefin is coordinated only with one C = C bond (dihapto link). - The reaction of Pd(acac)2 with either Pd[P(i-C3H7)3]2 or P(i-C3H7)3 leads to Pd(acac)2P(i-C3H7)3 (17) which contains one O,O-bonded and one C-bonded acetylacetonate ligand.
    Notes: Bei den Reaktionen der Palladium(II)-Komplexe [2-RC3H4Pd]2(OCOR′)2 [R = H, CH3, i-C3H7, t-C4H9 und R′ = CH3 (3), C6H5 (7), CF3 (9)] mit der äquimolaren Menge Pd[P(i-C3H7)3]2 in Hexan entstehen in sehr guter Ausbeute die Zweikernkomplexe (2-RC3H4)(OCOR′)Pd2[P(i-C3H7)3]2 (6, 8, 10), in denen Palladium in der Oxidationszahl +1 vorliegt. Die Synthese von (C5H5)(OCOCH3)Pd2[P(i-C3H7)3]2 (15) geht aus von den Diolefin-Komplexen[Cl(C6H8)Pd]2-(OCOCH3) 2 (11) und [Cl(C7H10)Pd]2(OCOCH3)2 (12), die mit TlC5H5 zu C5H5Pd(dien)-OCOCH3 [dien = 1,3-C6H8 (13), 1,3-C7H10 (14)] reagieren. Aus 13 oder 14 und Pd[P(i-C3H7)3]2 entsteht 15. In den Komplexen 11 - 14 ist das Diolefin nur über eine C = C-Bindung (dihapto) koordiniert. - Bei der Reaktion von Pd(acac)2 mit Pd[P(i-C3H7)3]2 oder P(i-C3H7)3 entsteht die Verbindung Pd(acac)2P(i-C3H7)3 (17), die einen O,O-gebundenen und einen C-gebundenen Acetylacetonatliganden enthält.
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  • 9
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Basic Metals, XXX. Reactivity and Dynamics of the Complexes C5H5Co(PR3)2 (R = Me, Et), (C5H4R)Co(PMe3)2, and C5H3RR)Co(PMe3)2: Influence of Steric Effects on the Lewis Basicity of Electron-rich MetalsThe complex C5H5Co(PMe3)2 (1) reacts with secondary and tertiary alkyl halides RX (R = CHMe2, CMe3. CMe2Et) to give the cations [(C5H4R)CoH(PMe3)2]+ which after reduction with NaH form the neutral compounds (C5H4R)Co(PMe3)2) (5-7). These are used as starting materials for the preparation of the disubstituted complexes [C5H3RR)CoH(PMe3)2]PF6 (15-17), (C5H3RR)Co(PMe3)2) (18-20) und [(C5H3RR)CoCH3(PMe3)2] 1 (21-23) (R = CHMe2, CMe3). In the compounds with R = R= CMe3 rotation about that metal-ring bond is so hindered the rigid conformers are present at 25-100°C. Similarly, a frozen conformation of the complex [C5H3(CHMe2)CMe3]Co(PMe3)2 (19) is evident below -10°C. The preparation of the complexes [C5H3RR)CoH(PMe3)2]PF6 (26-28), [C5H3(SiMe3)R]Co(PMe3)2 (27-29) (R = H, CHMe2) and C5H5Co(PEt3)2 (10) is also described and their dynamics as well as their reactivity are investigated.
    Notes: Der Komplex C5H5Co(PMe3)2 (1) reagiert mit sekundären und tertiären Alkylhalogeniden RX (R = CHMe2, CHe3, CMe2Et) zu den Kationen [(C5H4R) CoH(PMe3)2]+, die nach Reduktion mit NaH die Neutralverbindungen (C5H4Co(PMe3)2) (5-7) ergeben. Aus diesen werden die zweifach ringsubstituierten Komplexe [C5H3RR′)CoH(PMe3)2]PF6 (15-17), (C5H3RR′)Co(PMe3)2) (18-20) und [(C5H3RR′)CoCH3(PMe3)2] 1 (21-23) (R′ = CHMe2, CMe3) Synthetisiert. In den Verbindungen mit R = R′ =CMe3 ist die Rotation um die Metall-Ring-Bindung so stark behindert, daß bei 25-100°C starre Konformere vorliegen. Für [C5H3(CHMe2CMe3]Co(PMe3)2 (19) ist unterhalb -10°C ebenfalls eine eingefrorene Konformation nachweisbar. Die Komplexe [C5H3(SiMe3)R)CoH(PMe3)2]PF6 (26-28), [C5H3(SiMe3)R)]CoH(PMe3)2 (27-29) (R = H, CHMe2) und C5H5Co(PEt3)2 (10) werden ebenfalls dargestellt und ihr dynamisches Verhalten sowie ihre Reaktivität untersucht.
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  • 10
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Basic Metals, XXXI1). Preparation of Stable Diorganyl-, Organyl(trifluoroacetato)-, and Bis(trifluoroacetato)cobalt(III) CompoundsThe dimethylcobalt(III) compounds (C5H3RR')Co(CH3)2PR3″ (R = H, CHMe2; R' = H, CHMe2, CMe3; R″ = Me, Et) (1-6) have been prepared from [(C5H3RR')CoCH3(PR3″)2]I and LiCH3. They react with CF3CO2H under elimination of CH4 to give C5H5CoCH3(OCOCF3)PR3″ (7, 8) und (C5H3RR')Co(OCOCF3)2PR3″ (9-13). Complex C5H5CoCH3(C6H5)PMe3 (16)is formed from C5H5CoCH3(OCOCF3)PMe3 (7) and LiC6H5, whereas from C5H5Co(OCOCF3)2PMe3 (9) and LiC6H5 the very labile compound C5H5Co(C6H5)2PMe3 (15) is obtained. 16 reacts with an equimolar amount of CF3CO2H by cleavage of the Co—C6H5 and not of the Co—CH3 bond.
    Notes: Die Dimethylcobalt(III)-Verbindungen (C5H3RR')Co(CH3)2PR3″ (R = H, CHMe2; R' = H, CHMe2, CMe3; R″ = Me, Et) (1-6) werden aus [(C5H3RR')CoCH3(PR3″)2]I und LiCH3 synthetisiert. Sie reagieren mit CF3CO2H unter Abspaltung von CH4 zu C5H5CoCH3(OCOCF3)3″ (7, 8) und (C5H3RR')Co(OCOCF3)23″ (9-13). Der Komplex C5H5CoCH3(C6H5)PMe3 (16) entsteht aus C5H5CoCH3(OCOCF3)PMe3 (7) und LiC6H5, während aus C5H5Co(OCOCF3)2PMe3 (9) und LiC6H5 die sehr labile Verbindung C5H5Co(C6H5)2PMe3 (15) gebildet wird. 16 reagiert mit einer äquimolaren Menge CF3CO2H unter Spaltung der Co—C6H5- und nicht der Co—CH3-Bindung.
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