Synthesis binuclear complexes

Transition metal atoms in the synthesis of binuclear complexes. E. P. Kiindig, M. Moskvits and... 

Luminescent gold(l) acetylide complexes. Photophysical and photoredox properties and crystal structure of [ Au(C = CPh) 2 (p-Ph2PCH2CH2PPh2)]. Journal of the Chemical Society, Dalton Transactions, 2929-2932 (d) Che, C.-M., Wong, W.-T., Lai, T.-F. and Kwong, H.-L. (1989) Novel luminescent binuclear gold(I) isocyanide complexes. Synthesis, spectroscopy, and X-ray crystal structure of Au2(dmh)(CN)2 (dmb = 1,8-di-isocyano-p-menfhane). Journal of the Chemical Society, Chemical Communications, 243-244. 

In addition to group 6 metal heterocarbonyl complexes, some thioketone complexes of other metals have also been prepared by the substitution route. The synthesis of the binuclear complex [Mn(CO)2 S = C(Ph)[(T75-C5FLt) Mn(CO)3] (775-C5H5)] (5) was achieved by reaction of [Mn(CO)2(thf) ( -CsHs)] with cymantrenyl(phenyl)thioketone." Similarly, the tetracar-... 

The reaction of imidazole-4,5-dicarbaldehyde with 2-aminoethylpyridine in the presence of copper(II) chloride has enabled the preparation of a binuclear complex (equation 2).29 A more common class of binuclear complex is based on template reactions of a phenolic dialdehyde with various amines and includes the copper complexes (14)30 31 and (15).32 Reactions of this type can be extended to the synthesis of macrocyclic binuclear complexes such as (16).33,34... 

Another broad class of compounds are the bridged carbene complexes. These compounds contain two identical or two different metal centers with the carbene centers bonded to both of the metal atoms in a bridging relationship. However, these binuclear complexes generally do not show classical carbene reactivity and will therefore not be discussed further, except to mention briefly the special case of the titanium-aluminum complex (3) developed by Tebbe and Grubbs and their coworkers.101 This, and related complexes, has proven to be particularly useful in organic synthesis, although its principal importance is in reactions other than cyclopropanations. 

The formation of the unsaturated intermediate Run(OEP) from the hydrido-complex RumH(OEP) is supposed to occur from a LMCT excited state. As a consequence, the dimeric [RuH(OEP)]2 with a metal-metal interaction is formed [245]. Irradiation of some systems containing Fein(Por)N3 leads to p-nitrido bridged binuclear mixed-valence complexes [(Por)Fem-N-Fe,v(Por)] [134, 162], In both cases photochemistry was used as a conventional preparative route for synthesis of the binuclear complexes. 

Lehn, J.-M. Pine, S. H. Watanabe, E. I. Willard, A. K. Binuclear cryptates. Synthesis and binuclear cation inclusion complexes of bis-tren macrobicyclic ligands, J. Am. Chem. Soc. 1977, 99, 6766-6768. 

The main emphasis of our EC project is in electrocatalytic C02 reduction, where we explore synthetic pathways for novel binuclear Co complexes with tetra-azamacrocyclic ligands and their use in electrochemical measurements and synthesis. Although several routes for ligand synthesis have been briefly described in the literature, we find upon repeated attempts that well-characterised samples are hard to obtain. In one case (bis-dioxocyclam XI) We have obtained a pure product. In addtion, the rotating-ring disk electrode has been introduced in this study for obtaining kinetic information on mono-and binuclear complexes. For their use in anhydrous media, water-free compelxes have been prepared. 

One of the most general and useful methods of access to (tj6-arene)ruthenium(H) complexes is based on the dehydrogenation of cyclo-hexadiene derivatives by ethanolic solutions of RuC13 xH20 (6). This method has been developed for the synthesis of binuclear complexes 1 by Zelonka and Baird (7) for benzene (la) and by Bennett and co-workers (8-10) for para-cymene (lb), a useful starting material (10), and substituted benzene derivatives, such as xylene, mesitylene (9), or 1,3,5-triphenylbenzene (11) [Eq. (1)]. The chloride ligands of complexes 1 can... 

Allenylidene complexes, synthesis /z-allenylidene complexes, 225-227 binuclear compounds, 225, 225... 

Dihydropyridinyl carbene complexes, synthesis of binuclear compounds, 208... 

---