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  • 1
    Publication Date: 1987-06-01
    Print ISSN: 0276-7333
    Electronic ISSN: 1520-6041
    Topics: Chemistry and Pharmacology
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Organometallics 6 (1987), S. 1169-1172 
    ISSN: 1520-6041
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
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  • 3
    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, XXXVII. Bridge-Exchange Reactions with Dinuclear μ-(Cyclopentadienyl)-dipalladium Complexes: Synthesis of Sandwich-like Heterometallic Pd2Cr and Pd2Mo ClustersThe dimetal sandwich complexes (C5H5)2Pd2(PR3)2 (I) react with carboxylic acids R'CO2H and thiols R'SH by exchanging one cyclopentadienyl bridge to yield the compounds (C5H5)(OCOR')-Pd2(PR3)2 (1-6) and (C5H5)(SR')Pd2(PR3)2 (7-12). Displacement of the cyclopentadienyl and not of the allyl ligand also occurs in the reactions of (C5H5)(2-RC3H4)Pd2[P(iPr)3]2 (II) with R'CO2H and R'SH with formation of the dinuclear μ-(allyl)-dipalladium compounds (2-RC3H4)-(OCOR')Pd2[P(iPr)3]2 (13-23) and (2-RC3H4)(SR')Pd2[P(iPr)3)2 (24-27). The reaction of (C5H5)-(2-MeC3H4)Pd2(P(iPr)3]2 (IIa) with terephthalic acid leads to the tetranuclear complex 28. The trinuclear heterometallic clusters 29, 30 are obtained by bridge-exchange starting from (C5H5)(OCO-tBu)Pd2[P(iPr)3]2 (4) and Na[C5H5Cr(CO)3] or Na[C5H5Mo(CO)3], respectively.
    Notes: Die Dimetall-Sandwichkomplexe (C5H5)2Pd2(PR3)2 (I) reagieren mit Carbonsäuren R'CO2H und Thiolen R'SH unter Austausch einer Cyclopentadienyl-Brücke zu den Verbindungen (C5H5)-(OCOR')Pd2(PR3)2 (1-6) und (C5H5)(SR')Pd2(PR3)2 (7-12). Bei den Umsetzungen der Komplexe (C5H5)(2-RC3H4)Pd2[P(iPr)3]2 (II) mit R'CO2H und R'SH wird ebenfalls der Cyclopentadienyl- und nicht der Allyl-Ligand verdrängt, so daß die zweikernigen μ-(Allyl)-dipalladium-Verbindungen (2-RC3H4)(OCOR')Pd2[P(iPr)3]2 (13-23) und (2-RC3H4)(SR')Pd2[P(iPr)3]2 (24-27) entstehen. Die Reaktion von (C5H5)(2-MeC3H4)Pd2[P(iPr)3]2 (IIa) mit Terephthalsäure führt zu dem Vierkernkomplex 28. Durch Brückenaustausch sind aus (C5H5)(OCO-tBu)Pd2[P(iPr)3]2 (4) und Na[C5H5Cr(CO)3] bzw. Na[C5H5Mo(CO)3] die dreikernigen heterometallischen Cluster 29, 30 zugänglich.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 365-372 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The reaction of the cyclopentadienyl- and halide-bridged dinuclear complexes (μ-C5H5)(μ-X)Pd2(PEt3)2 (1a, b) und (μ-C5H5)(μ-X)Pd2(piPr3)2(2a, b) mit CO, CNR (R=CH3, C6H5, p-CH3C6H4), SO2 und C2(CO2Me)2 leads almost quantitatively to the formation of the compounds C5H5(PR3)Pd(μ-E)Pd(PR3)X (3, 4, 6-11), in which the bridging ligand E E [CO, CNR, SO2, C2(CO2Me)2] is unsymmetrically linked to the two electronically different molecular fragments C5H5(PR3)Pd and Pd(PR3)X. The addition of E occurs without cleavage of the metal-metal bond. C5H5(PEt3)Pd(μ-CO)Pd(PEt3)Br (3b) reacts smoothly with SO2 to produce C5H5(PEt3)Pd(μ-SO2)Pd(PEt3)Br (9b); exchange of the bridging ligand in the reverse direction does not occur. The structure of the complexes C5H5(PiPr3)Pd(PiPr3)Cl (4a) und 9b has been determined by X-ray analysis.
    Notes: Die Reaktion der Cyclopentadienyl- und Halogen-verbrückten Zweikernkomplexe (μ-C5H5)(μ-X)Pd2(PEt3)2 (1a, b) und (μ-C5H5)(μ-X)Pd2(piPr3)2(2a, b) mit CO, CNR (R=CH3, C6H5, p-CH3C6H4), SO2 und C2(CO2Me)2 führt nahezu quantitativ zu den Verbindungen C5H5(PR3)Pd(μ-E)Pd(PR3)X (3, 4, 6-11), in denen der Brückenligand E [CO, CNR, SO2, C2(CO2Me)2] unsymmetrisch an die beiden elektronisch ungleichen Molekülfragmente C5H5(PR3)Pd und Pd(PR3)X gebunden ist. Die Addition von E verläuft ohne Spaltung der Metall-Metall-Bindung. C5H5(PEt3)-Pd(μ-CO)Pd(PEt3)Br (3b) reagiert mit SO2 sehr rasch zu C5H5(PEt3)Pd(μ-SO2)Pd(PEt3)Br (9b); ein Brückenaustausch in umgekehrter Richtung ist nicht möglich. Die Struktur der Komplexe C5H5(PiPr3)Pd(PiPr3)Cl (4a) und 9b wird durch Röntgenstrukturanalyse bestimmt.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 261-274 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Basic Metals, XLVI. Synthesis of Novel Carbenoid and Yliderhodium (III) Complexes from C5H5Rh(C2H4)PMe3, and the Crystal Structure of [C5H5RhCH2NC5H5(PMe3)I] PF6C5H5Rh(C2H4)PMe3 (1) reacts with CH2I2, CH2Br2, CH2ICI and CH2ICN to yield the carbenoidrhodium(III) Compounds [C5H5RhCH2X(PMe3)X′] (2-5). From 1 and [CHX3 (X = Br, I) the complexes [C5H5RhCHX2(PMe3)X] (6, 7) are obtained. The reactions of [C5H5RhCH2I-(PMe3)I] (2) with NaOCH3, NaSR (R = CH3, C6H5), KSCN and Na[AlH2(OC2H4OMe)2] (Red-al) lead to the compounds [C5H5RhCH2OCH3(PMe3)I] (9), [C5H5RhCH2SR(PMe3)SR] (11, 12), [C5H5RhCH2SCN(PMe3)I] (13), and [C5H5RhCH3(PMe3)I] (14). With NaOH in C6H6/H2O in presence of a phase-transfer catalyst isomerization of 2 to give [C5H5Rh-(CH2PMe3)I2] (10) occurs. Substitution of the carbon-bonded iodide in 2 by PPh3, PiPr3, NEt3, pyridine, AsPh3, SMe2, and tetrahydrothiophene gives the complexes [C5H5RhCH2L(PMe3)I]X (15-21) in which the ylides CH2PPh3, CH2PiPr3, CH2NEt3, CH2NC5H5, CH2AsPh3, CH2SMe2, and CH2SC4H8 are formed as ligands. The crystal structure of 18 (L = NC5H5) has been determined. The result shows that the rhodium is octahedrally coordinated and that the Rh—C and C—N distance in the RhCH2NC5H5 group correspond to single bond lengths. The Rh—C(C5H5) distances vary between 217 (2) and 224 (3) pm thus reflecting the different trans influence of the ligands I, PMe3, and CH2NC5H5.
    Notes: C5H5Rh(C2H4)PMe3 (1) reagiert mit CH2I2, CH2Br2, CH2ICI und CH2ICN zu den Carbenoidrhodium(III)-Verbindungen [C5H5RhCH2X(PMe3)X′] (2-5). Aus 1 und CHX3 (X = Br, I) entstehen die Komplexe [C5H5RhCHX2(PMe3)X] (6, 7). Durch Reaktion von [C5H5RhCH2I-(PMe3)I] (2) mit NaOCH3, NaSR (R = CH3, C6H5), KSCN und Na[AlH2(OC2H4OMe)2] (Redal) werden die Verbindungen [C5H5RhCH2OCH3(PMe3)I] (9), [C5H5RhCH2SR(PMe3)SR] (11, 12), [C5H5RhCH2SCN(PMe3)I] (13) und [C5H5RhCH3(PMe3)I] (14) erhalten. Bei der Einwirkung von NaOH auf 2 in C6H6/H2O in Gegenwart eines Phasen-Transfer-Katalysators tritt eine Isomerisierung zu [C5H5Rh(CH2PMe3)I2] (10) ein. Die Substitution des C-gebundenen Iodids in 2 durch PPh3, PiPr3, NEt3, Pyridin, AsPh3, SMe2 und Tetrahydrothiophen ergibt die Komplexe [C5H5RhCH2L(PMe3)I]X (15-21), in denen die Ylide CH2PPh3, CH2PiPr3, CH2NEt3, CH2NC5H5, CH2AsPh3, CH2SMe2 und CH2SC4H8 als Liganden vorliegen. Die Kristallstruktur von 18 (L = NC5H5) wurde bestimmt. Das Ergebnis zeigt, daß das Rhodium oktaedrisch koordiniert ist und die Rh—C- und C—N-Abstände in der RhCH2NC5H5-Gruppierung Einfachbindungslängen entsprechen. Die Rh—C(C5H5)-Abstände liegen zwischen 217 (2) und 224 (3) pm und spiegeln den unterschiedlichen trans-Einfluß der Liganden I, PMe3 und CH2NC5H5 wider.
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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: Stepwise Formation of Heterometallic Trinuclear and Tetranuclear Clusters from Dipalladium(I) Compounds and Carbonylmetalate Anions. The Crystal and Molecular Structure of (C5H5)2(CO)3(PiPr3)2MoPd2The carboxylate- or halide-bridged dinuclear complexes (μ-C5H5)(μ-X)Pd2(PR3)2 (1, 2a-c) react with Na[C5H5M(CO)3] (M = Cr, Mo, W), Na[Co(CO)4], and [Na(diglyme)2][V(CO)6] to produce the heterometallic trinuclear clusters 3-11. The structure of the MoPd2 compound (C5H5)2(CO)3(PiPr3)2MoPd2 (4) which is also obtained from (μ-C5H5)(μ-tBuCO2)-Pd2(PiPr3)2 (1) and C5H5Mo(CO)3SiMe3 has been determined by X-ray analysis. 4 contains a tetrahedral MoPd2C framework, the carbon atom of which belongs to a triply-bridging CO group. The Pd - Pd and Pd-Mo edges of the tetrahedron are further bridged by an “allyl-ene” type cyclopentadienyl ring and by two semi-bridging CO ligands. Similar tri-nuclear clusters 15-18 are formed from (μ-2-MeC3H4)(μ-X)Pd2(PiPr3)2 (14a-c) and Na[C5H5M(CO)3] (M = Cr, Mo, W) or Na[Co(CO)4], respectively. Displacement of the cyclopentadienyl bridge in 4 and 6-8 by chloride and subsequent reaction with Na[C5H5M-(CO)3] produces the Pd2M2 clusters 22 and 23a-c. The bonding properties of the hetero-metallic trinuclear and tetranuclear clusters (possessing 44 and 58 valence electrons, respectively) is briefly discussed.
    Notes: Durch Umsetzung der carboxylat- bzw. halogenid-verbrückten Zweikernkomplexe (μ-C5H5)(μ-X)Pd2(PR3)2 (1, 2a-c) mit Na[C5H5M(CO)3] (M = Cr, Mo, W), Na[Co(CO)4] und [Na(diglyme)2][V(CO)6] werden die Heterometall-Dreikerncluster 3-11 synthetisiert. Der Aufbau der MoPd2-Verbindung (C5H5)2(CO)3(PiPr3)2MoPd2 (4), die auch aus (μ-C5H5)(μ-tBuCO2)Pd2(PiPr3)2 (1) und C5H5Mo(CO)3SiMe3 erhältlich ist, wurde durch eine Röntgen-strukturanalyse bestimmt. 4 besitzt ein tetraedrisches MoPd2C-Gerüst, dessen Kohlenstoff-atom von einer dreifach-verbrückenden CO-Gruppe stammt. Die Pd- Pd- und Pd- Mo-Kanten des Tetraeders sind durch einen „allyl-en“-artig koordinierten C5H5-Ring und zwei semi-verbrückende CO-Liganden überbrückt. Ähnlich aufgebaute Dreikerncluster 15-18 entstehen ausgehend von (μ-2-MeC3H4)(μ-X)Pd2(PiPr3)2 (14a-c) und Na[C5H5M(CO)3] (M = Cr, Mo, W) bzw. Na[Co(CO)4]. Durch Austausch der Cyclopentadienyl-Brücke in 4 und 6-8 gegen Chlorid und nachfolgende Reaktion mit Na[C5H5M(CO)3] können die Pd2M2-Vierkerncluster 22 und 23a-c hergestellt werden. Die Bindungsverhältnisse der heterometallischen Dreikern- und Vierkern-Cluster (mit 44 bzw. 58 Valenzelektronen) werden kurz diskutiert.
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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: Copper(II) Acetate as a Building Block of Heterometallic Dinuclear Complexes with a Cu—Mo and Cu—W Bond. The x-ray Crystal Structures of C5H5(CO)2Mo(μ-O2CMe)2Cu(4-MeC5H4N) and C5H5W(CO)3OC(O)MeThe reactions of the dimeric copper(II) acetate adducts L2Cu2(μ-O2CMe)4 (3a-c) with Na[M(CO)3C5H5] (M = Mo, W) lead to the formation of the heterometallic dinuclear complexes C5H5(CO)2M(μ-O2CMe)2Cu(L) (4a-c, 7a, b). For M = W, the mononuclear compound C5H5W(CO)3OC(O)Me (8) has been isolated as a minor product. The X-ray structural analysis of 4b (M = Mo, L = 4-methylpyridine) reveals that the two metal atoms are linked by a direct Cu—Mo bond and are also bridged by two acetate units. On the same route as 4b, the dinuclear complexes C5H5(CO)2Mo(μ-O2CCF3)2Cu(4-MeC5H4N) (5), C5Me5(CO)2Mo(μ-O2CMe)2Cu(4-MeC5H4N) (6), and C5H5(CO)2W(μ-O2CCF3)2Cu(4-MeC5H4N) (9) have been obtained. Compound 8 which owing to the X-ray analysis has a four-legged-piano-stool structure is accessible almost quantitatively on reaction of C5H5W(CO)3CH3 (11) with CH3CO2H/HBF4 followed by deprotonation of the isolated intermediate [C5H5W(CO)3(CH3CO2H)]BF4 (12) with K2CO3. Starting with C5H5Mo(CO)3CH3 (13) and CH3CO2H/HBF4, the molybdenum compound [C5H5Mo(CO)3(CH3CO2H)]BF4 (14) and from this and K2CO3 a mixture of C5H5Mo(CO)3OC(O)Me (15) and C5H5Mo(CO)2(η2-O2CMe) (16) are prepared. That 8 and 15 are intermediates in the formation of the dinuclear (Cu-Mo) and (Cu-W) complexes from 3 and Na[M(CO)3C5H5] has been confirmed by independent synthesis of 4b and 7b from C5H5M(CO)3OC(O)Me, MeCO2Cu and 4-methylpyridine. Similarly, the bis-μ-(benzoato) complexes C5H5(CO)2M(μ-O2CPh)2Cu(4-MeC5H4N) (20, 23) have been obtained. The reactions of 4b and 7b with PR3 (R = Ph, Me), C2Ph2 (in presence of HBF4), and thioacetic acid produce the compounds cis-[C5H5M(CO)2(PR3)OC(O)Me] (25-28), [C5H5M(CO)(C2Ph2)2]BF4 (29, 30), and C5H5Mo(CO)2(η2-OSCMe) (31).
    Notes: Die Reaktionen der dimeren Kupfer(II)-acetat-Addukte L2Cu2(μ-O2CMe)4 (3a-c) mit Na[M(CO)3C5H5] (M = Mo, W) führen zu den heterometallischen Zweikernkomplexen C5H5(CO)2M(μ-O2CMe)2Cu(L) (4a-c, 7a, b). Als weiteres Produkt wird für M = W die einkernige Verbindung C5H5W(CO)3OC(O)Me (8) isoliert. Die Röntgenstrukturanalyse von 4b (M = Mo, L = 4-Methylpyridin) zeigt, daß die beiden Metallatome durch zwei Acetatbrücken verknüpft sind und eine Mo-Cu-Bindung vorliegt. Auf gleichem Wege wie 4b sind die Zweikernkomplexe C5H5(CO)2Mo-(μ-O2CCF3)2Cu(4-MeC5H4N) (5), C5Me5(CO)2Mo(μ-O2CMe)2Cu-(4-MeC5H4N) (6) und C5H5(CO)2W(μ-O2CCF3)2Cu(4-MeC5H4N) (9) erhältlich. Verbindung 8, die nach der Kristallstrukturanalyse eine “Four-legged-piano-stool”-Struktur besitzt, bildet sich fast quantitativ durch Umsetzung von C5H5W(CO)3CH3 (11) mit CH3CO2H/HBF4 und anschließende Deprotonierung der isolierten Zwischenstufe [C5H5W(CO)3(CH3CO2H)]BF4 (12) mit K2CO3. Aus C5H5Mo(CO)3CH3 (13) und CH3CO2H/HBF4 entsteht analog [C5H5Mo(CO)3(CH3CO2H)]BF4 (14) und daraus mit K2CO3 ein Gemisch von C5H5Mo(CO)3OC(O)Me (15) und C5H5Mo(CO)2(η2-O2CMe) (16). Daß 8 und 15 Intermediate bei der Darstellung der (Cu—Mo)- und (Cu—W)-Zweikernkomplexe aus 3 und Na[M(CO)3C5H5] sind, wird durch die unabhängige Synthese von 4b und 7b aus C5H5M(CO)3OC(O)Me, MeCO2Cu und 4-Methylpyridin bestätigt. In entsprechender Weise sind die Bis-μ-(benzoato)-Komplexe C5H5(CO)2M(μ-O2CPh)2Cu(4-Me-C5H4N) (20, 23) zugänglich. Die Reaktionen von 4b bzw. 7b mit PR3 (R = Ph, Me), C2Ph2 (in Gegenwart von HBF4) und Thioessigsäure ergeben die Verbindungen cis-[C5H5M(CO)2(PR3)-OC(O)Me] (25-28), [C5H5M(CO)(C2Ph2)2]BF4 (29, 30) und C5H5Mo(CO)2(η2-OSCMe) (31).
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  • 8
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 9
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 10
    ISSN: 0570-0833
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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