The heteroleptic complex [(HOOC-tpy)Ru(tpy-NH 2 )](PF 6 ) 2 (tpy = 2,2Ј;6Ј,2ЈЈ-terpyridine) has been incorporated into a multicomponent system with ferrocene moieties attached on either the N-terminal end or the C-terminal end and on both ends of the ruthenium complex. Electrochemical studies reveal almost noninteracting subunits in the oligonuclear sys-
Ferrocene-containing tripeptides with one to two ferrocene building blocks were prepared by solid-phase peptide synthesis (SPPS) using Fmoc-protected 1Ј-aminoferrocene-1-carboxylic acid (Fca). The conformations of the tripeptides were analysed by spectroscopic and theoretical methods. The im-
This overview highlights recent progress in the field of selective construction of linear, oligonuclear transition-metal complexes by using solid-phase synthesis procedures. Two general protocols have been identified: formation of coordinative bonds between metal centres and bridging ligands and formation of covalent bonds between preformed kinetically inert transition-metal-containing building blocks in the chain growth step. Currently available suitable building blocks for the second approach are based on ferrocene units, bis(terpyridine)-ruthenium(II) moieties or metal porphyrins.
Reaction of C-ferrocenyl-substituted aminocarbene tungsten complex 1 with [bis(trimethylsilyl)methylene]chlorophosphane (2) and triethylamine yielded 2H-azaphosphirene complex 3 in good yield. Reaction of complex 3 with aryl nitriles 4a-c, N-piperidinonitrile (4d), and acetonitrile (4e) in the presence of ferrocenium hexafluorophosphate yielded regioselectively 2H-1,4,2-diazaphosphole complexes 5a-e through single-electron-transfer-induced ring expansion to-
Selective macrocyclization of 1,1Ј-ferrocenediylbis(aminocarbene complex) 1 was achieved by its reaction with chloro-(methylene)phosphane 2 and triethylamine at ambient temperature, thus yielding the novel diaminophosphane-bridged [5]ferrocenophane bis(carbene complex) 3. This trimetallic species, which combines the structural features of both ferro-
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