The meta-diaminoaryl ferrocene Fe[eta(5)-C5H4(NCNH)](2) [NCNH = 1-C6H3(CH2NMe2)(2)-3,5] (3) can be synthesised by the reaction of Fe[eta(5)-C5H4(ZnCl)](2) (1) with I-C6H3(CH2NMe2)(2)-3,5 (2) in a 1:2 molar ratio in the presence of catalytic amounts of [Pd(PPh3)(2)]. The two meta-dimaminoaryl NCNH pincer units in 3 can be used to assemble multimetallic complexes. Thus, 3 produces on reaction with (BuLi)-Bu-t and (Me2S)(2)PdCl2 trimetallic Fe[eta(5)-C5H4(NCN-4-PdCl)](2) {NCN = 1-C6H2(CH2NMe2)(2)-3,5} (6) along with heterobimetallic Fe[eta(5)-C5H4(NCNH)][eta(5)-C5H4(NCN-4-PdCl)] (5). Complex 6 contains two bis-ortho-chelated pincer NCN-PdCl units, whereas 5 possesses one bis-ortho-chelated NCN pincer entity and one non-metallated NCNH moiety. Complex 6 is the first example in organometallic chemistry in which two bis-ortho-chelated diaminoaryl palladium units are bridged via the respective para C-atoms spanned by a redox-active ferrocenyl building block. (C) 2003 Elsevier B.V. All rights reserved.
Organometallic π-Tweezers, NCN Pincers, and Ferrocenes as Molecular “Tinkertoys” in the Synthesis of Multiheterometallic Transition-Metal Complexes
作者:Heinrich Lang、Rico Packheiser、Bernhard Walfort
DOI:10.1021/om058042p
日期:2006.4.1
describes the synthesis, reaction chemistry, structures, and bonding of early−late heterodi-, heterotri-, and heterotetrametallic transition-metal complexes by applying the molecular “Tinkertoy” approach. As connecting units between the different metal atoms, π-conjugated carbon-rich organic and/or inorganic groups can be used. The electrochemical behavior of such one-dimensional molecular wire molecules