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Heterobimetallic Fe-Pd and Fe-Pt NCN pincer complexes (NCN = [C6H2(CH2NMe2)2-2 ,6]-)

The meta-diaminoaryl ferrocenes Fc-NCN-H (3) and Fc-C{triple bond, long}C-NCN-H (5) (Fc = (η5-C5H5)(η5-C5 H4)Fe, NCN-H = C6H3(CH2NMe2)2-3, 5) can be used as precursors in the preparation of heterobimetallic transition metal complexes of structural type Fc-NCN-MX (NCN = [C6H2(CH2NMe2)2-2 ,6]-; MX = PdCl (7), PtCl (8), PtI (9)) and Fc-C{triple bond, long}C-NCN-MX (MX = PdCl (11), PdI (12), PtCl (13)), respectively. They are accessible by applying different synthesis procedures, including oxidative addition and metallation-transmetallation processes. Cyclovoltammetric studies show that the ferrocene moieties in 3, 5, 7-9 and 11-13 can reversibly be oxidised. The potential of the Fe(II)/Fe(III) redox couple decreases with increasing electron density at the NCN pincer unit. The use of 8 as a possible (electro)chemical sensor in the detection of SO2 is discussed as well. The solid-state structures of 8 and 13 are reported. The crystals of 8 contain two molecules of 8 in the asymmetric unit. The plane of the C6H2 moiety is with 27.2(3)° and 38.2(3)° tilted towards the C5H4 entity, while in 13 an angle of 45.9(3)° can be found. The d8-electron configured platinum atoms possess a somewhat distorted square-planar surrounding, setup by two Me2NCH2 ortho-substituents, the NCN Cipso carbon atom and the chloride ligand.

Organometallic π-tweezers, NCN pincers, and ferrocenes as molecular "Tinkertoys" in the synthesis of multiheterometallic transition-metal complexes

This review 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 differ

Ferrocene-bridged Pd-NCN pincer complexes

The meta-diaminoaryl ferrocene Fe[η5-C5 H4(NCNH)]2 [NCNH=1-C6H3 (CH2NMe2)2-3,5] (3) can be synthesised by the reaction of Fe[η5-C5H4(ZnCl)] 2 (1) with I-C6H3(CH2 NMe2)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 t BuLi and (Me2S)2PdCl2 trimetallic Fe[η5-C5H4(NCN-4-PdCl)]2 {NCN=1-C6H2(CH2NMe2) 2-3,5} (6) along with heterobimetallic Fe[η5 -C5H4(NCNH)][η5-C5 H4(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.