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.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19851180125
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