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  • 1
    ISSN: 0009-2940
    Keywords: Phospha- and arsaalkene rhodium complexes ; Metalla heterocycle containing RhAs3 ; Rhodium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: CH2=PPH and CH2=AsPh as Ligands Coordinated to Rhodium. Crystal and Molecular Structure of C5Me5Rh(η2-CH2PPh)(CO) and C5Me5(CO)Rh(AsPh)3C5Me5RhCH2I(CO)I (1) reacts with excess LiPHPh or LiAsHPh to give the complexes C5Me5Rh(η2-CH2EPh)(CO) (2: E = P; 3: E = As). The C—P bond length of the coordinated phosphaalkene in 2 is 174.0(4) pm and thus ca. 10 pm shorter than that of a C—P single bond. On standing in solution, the new heterocycle C5Me5(CO)Rh(AsPh)3 (4) is formed from 3. The X-ray analysis of 4 shows that the bonding distances and angles in the central nonplanar RhAs3 four-membered ring are very similar to thos in cyclo-(AsCF3)4.
    Notes: C5Me5RhCH2I(CO)I (1) reagiert mit überschüssigem LiPHPh oder LiAsHPh zu den Komplexen C5Me5Rh(η2-CH2EPh)(CO) (2: E = P; 3: E = As). Der C—P-Abstand des koordinierten Phosphaalkens in 2 ist mit 174.0(4) pm um ca. 10 pm kürzer als der einer C—P-Einfachbindung. Beim Stehenlassen in Lösung entsteht aus 3 teilweise der Heterocyclus C5Me5(CO)Rh(AsPh)3 (4), von dem die Struktur bestimmt wurde. Die Bindungsabstände und -winkel in dem zentralen, nicht planaren RhAs3-Vierring sind denen in cyclo-(AsCF3)4 sehr ähnlich.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1605-1617 
    ISSN: 1434-1948
    Keywords: Rhodium ; Carbenoide metal complexes ; Formaldehyde complexes ; Thioformaldehyde complexes ; Cyclopentadienyl complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The acetoxymethyl rhodium compounds [(η5-C5R5)Rh(CH2OAc)(L)I] (4, 13-16) which were prepared from the chloromethyl derivatives [(η5-C5R5)Rh(CH2Cl)(L)I] and sodium acetate in benzene/acetic acid as solvent, reacted with AgPF6 to give the chelate complexes [(η5-C5R5)Rh{ĸ2-C,O-CH2OC(Me)O}(L)]PF6 (19-23) in excellent yields. Treatment of these complexes with KOH in methanol led to the elimination of the acetyl group and to the formation of the formaldehyde compounds [(η5-C5R5)Rh(η2-CH2O)(L)] (24-27). The related thioformaldehyde complexes [(η5-C5Me5)Rh(η2-CH2S)(L)] (46, 47) and [(η5-C5H5)Rh(η2-CH2S)(PMe3)] (50) were obtained on a similar route. Studies on the reactivity of the formaldehyde derivatives revealed that the Rh-CH2O bond is rather labile and the CH2O ligand easily converted to a CO group.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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