Tetranuclear heterodimetallic metallamacrocyles with M-Sn(IV) (M = Mo or W) bonds. Crystal structures of {p[(CO)(3)MoC5H4C(O)](2)C6H4}{(Ph2Sn)(2)S} and {p-[(CO)(3)MoC5H4C(O)](2)C6H4}{(Ph2Sn)(2)CH2}

摘要

The dianions {[p-(CO)(3)MC5H4C(O)](2)C6H4}(2-) reacted with Ph2SnBr2 in a 1:2 or 1:1 ratio to give tetranuclear heterodimetallic complexes p-[(Ph2BrSn)(CO)(3)MC5H4C(O)](2)C6H4 (M = Mo (1) or W (2), respectively), and with CH2(SnPhBr2)(2) to yield tetranuclear heterodimetallic metallamacrocycles {p-[(CO)(3)MC5H4C(O)](2)C6H4} {(Ph2-nBrnSn)(2)CH2} (n = 1, M = Mo (5) and W (6); n = 0, M = Mo (7) and W (8), respectively). Only one bromide on the tin atom was replaced by the metallic anions owing to the electron-withdrawing groups on the cyclopentadienyl rings greatly decreasing the nucleophilicity of the metallic anions. Treatment of complexes 1 and 2 with Na2S.9H(2)O yielded the novel metallamacrocyclic complexes {p-[(CO)(3)MC5H4C(O)](2)C6H4} {(Ph2Sn)(2)S} (M = Mo (3) and W (4), respectively). All compounds have been characterized by elemental analyses, IR and H-1-NMR spectra. The crystal structures of complexes 3 and 7 determined by X-ray crystallography indicate a novel 14-membered organometallic metallamacrocyclic ring system in which two Mo-Sn units are linked by the bridging cyclopentadienyl ligand and the sulfur or carbon atom. In addition, the carbonyl group pi-system is coplanar with the adjacent cyclopentadienyl ring system, but markedly deviates from the bridging phenyl plane. (C) 2003 Elsevier Science B.V. All rights reserved. [References: 35]