ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Complex Chemistry of Polyfunctional Ligands, XXXVI: About Halogeno- and Pseudohalogeno-cobalt(I) Complexes of the Tritertiary Phosphine 1,1,1-Tris(diphenylphosphinomethyl)ethane\documentclass{article}\pagestyle{empty}\begin{document}$ [\mathop {{\rm Co}}\limits^{ + {\rm I}} ({\rm CO})_2 ({\rm R}_2 {\rm PCH}_2)_3 {\rm CCH}_3][\mathop {{\rm Co}}\limits^{ - {\rm I}} ({\rm Co})_4] $\end{document} (R = C6H5) 2 reacts with the alkali metal halides and pseudohalides MX(M = Na, K; X = Cl, Br, J) on ultraviolet irradiation to give the monomeric, paramagnetic (μeff ≍ 3 B.M.), tetrahedral cobalt(I) complexes XCo(R2PCH2)3CCH33 With CO the halogeno-cobalt(I) complexes 3a-c) yield the ionic, diamagnetic dicarbonyl compounds [Co(CO)2(R2PCH2)3]X(X = Cl, Br, J) 5. On the other hand the pseudohalogeno-cobalt(I) complexes 3d,e give with CO the non-ionic complex Co(NCO)(CO)2(R2PCH2C(CH3)CH2PR2 6. The potentially tridentate ligand CH3C(CH2PR2)3 Serves in it as a bidentate monometallic ligand. The halogeno- and pseudohalogeno-cobalt(I) complexes 3 are very air-sensitive. The forming of O2-complexes from the pseudohalogeno-cobalt(I) compounds 3d, e in the solid state has been shown qualitatively by the infrared spectra. In solution these O2complexes decompose to phosphine oxide-containing products. With 9,10-phenanthrenequinone, Co(NCO)(R2PCH2)3CCH3 (3d) gives also an oxidative addition product, the Paramagnetic Co(NCO)(C14H8O2(R2PCH2)2-C(CH3) CH2PR2 8 (μeff 2.97 B.M.). The compounds were characterized by their infrared and far infrared spectra.
Notes:
\documentclass{article}\pagestyle{empty}\begin{document}$ [\mathop {{\rm Co}}\limits^{ + {\rm I}} ({\rm CO})_2 ({\rm R}_2 {\rm PCH}_2)_3 {\rm CCH}_3][\mathop {{\rm Co}}\limits^{ - {\rm I}} ({\rm Co})_4] $\end{document} (R = C6H5) 2 setzt sich mit Alkalimetallhalogeniden und pseudohalogeniden MX (M = Na, K; X = Cl, Br, J, NCO, N3)unter UV-Bestrahlung zu den monomeren, paramagnetischen (μeff ≍ 3 B.M.), tetraedrischen Kobalt(I)-Komplexen XCo(R2PCH2CCH3 3um. Mit Co bilden die Halogeno-kobalt(I)-Komplexe 3a-c die ionischen, diamagnetischen Dicarbonylverbindungen [Co(CO)2(R2PCH2)CCH3]X (X = Cl, Br, J) 5. Die pseudohalogeno-kobalt(I)-Komplexe 3d, e reagieren dagegen mit CO jeweils zu dem nicht ionischen CO(NCO)(CO)2(R2PCH2C(CH3)CH2PR2 6 Der potentiell dreizähnige Ligand CH3C(CH2PR2)3 wirkt dabei lediglich zweifachkoordinierend-monometallisch. Die halogeno und Pseudohalogeno-kobalt(I) Komplexe 3 sind sehr oxidationsempfindlich. Bei den pseudohalogeno-kobalt(I)Komplexen 3d-e gelang es, im Festzustand die Bildung von O2-Komplexen qualitativ IR-spektroskopisch nachzuweisen. In Lösung zerfallen diese O2-Komplexe zu phosphinoxidhaltigen Produkten. 9,10-Phenanthrenchinon wird oxidativ an Co(NCO)(R2PCH2)3CCH3(3d) addiert. Es entsteht das paramagnetische Co(NCO)(C14H8O2)(R2PCH2)2C(CH3)CH2PR2 8 mit einem mittleren Spin von 2.97B. M. Die Verbindungen wurden IR- unf FIR- spektroskopisch untersucht.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19761090331
