ISSN:
0009-2940
Schlagwort(e):
Phosphametallacyclopropanes
;
Isolobal building blocks
;
Lewis basic behavior
;
Chemistry
;
Inorganic Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
Metal-Containing Heterocycles: Preparation, Properties, Reactions, LXXVII. - Synthesis, Structure and Reactivity of Phosphametallacyclopropanes with Isolobal ER (E = N,P,As,Sb) and Fe(CO)4 Building BlocksThe phosphidometallates \documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ Li_2 \left\{ {\left[ M \right]\dddot - PPh_2 } \right\} $\end{document} {[M] = (η5-C5H5)M-(CO)2}, resulting from the metal hydride complexes H[M]PPh2H [M = Cr (1), Mo (2), W (3)] by reduction with nBuLi, react with the geminal dihalides RECl2 to give the three-membered phosphametallacyclopropanes [ER = NC6F5 (M = Cr (1a), Mo (2a), W (3a)), PPh (M = Cr (1b), Mo (2b), W (3b)), PC6H11 (M = Cr (1c), Mo (2c), W (3c)), P-tBu (M = Cr (1d), Mo (2d), W (3d)), P(2,4,6-(tBu)3C6H2) (M = Cr (1e), Mo (2e), W (3e)), As(2,4,6-(tBu)3C6H2) (M = Cr (1f), Mo (2f), W (3f)), Sb-tBu (M = Cr (1g), Mo (2g))]. Reaction of Br2Fe(CO)4 with the corresponding dilithium compounds \documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ Li_2 \left\{ {\left[ M \right]\dddot - PPh_2 } \right\} $\end{document} affords the phosphido-bridged heterodimetallic complexes . According to X-ray structural analyses in 2a and 2f the P - E bond distances are shortened while the Mo - E bonds are significantly elongated compared to a single bond. (OC)5CrTHF is added to the Lewis basic E atom in 2b, 2d, and 2g with loss of THF to give P-tBu (4d), Sb-tBu (4g)]. By this reaction the antimony-containing ring 2g is kinetically stabilized. Because of the low basicity of the N atom in 2a no addition was observed. The ring skeleton of 4b and 4g, undergoes no change by Cr(CO)5 coordination as shown by X-ray structural analyses.
Zusätzliches Material:
2 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/cber.19911241005
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