Conformational behaviour of dinuclear Rh(I) complexes of the open-chain tetrapyrrolic ligand 2,2′-bidipyrrin (H2BDP)

Advances in the Chemistry of Dipyrrins and Their Complexes

“…The preparation of a series of earlier transition metal ion complexes expanded the list of known coordination geometries available to bis(dipyrrin)s. 91,184,240,241 A rhodium(I) cluster complex (4, shown previously in Figure 7) is the only example of non-κ 2 bonding of a metal ion by a bis(dipyrrin). 91 This lead to an investigation which showed that the rhodium reagents used in the preparation of bis(dipyrrinato) rhodium complexes affected the structure of the product in terms of the metal-to-ligand ratio.…”

“…The preparation of a series of earlier transition metal ion complexes expanded the list of known coordination geometries available to bis(dipyrrin)s. ,,, A rhodium(I) cluster complex ( 4 , shown previously in Figure ) is the only example of non-κ 2 bonding of a metal ion by a bis(dipyrrin) .…”

Cationic nickel porphyrinoids with unexpected reactivity

“…6 Using 2,2′-bidipyrrins like 3 7 for an analogous transformation provides an option for the preparation of metal 9-methylisocorroles like 4 . This ligand framework had been observed in serendipitously isolated rhodium and iridium complexes before, 8 however, no logical synthesis nor any understanding of the formation of such chelates has so far been developed. A metal template assisted oxidative ring closure reaction is indeed successful with the precursors 5 and 6 , and we report here about the synthesis and unexpected features of first cationic nickel( ii ) complexes 7 and 8 of such 9-methylisocorroles ( Scheme 1 ).…”

Iron Chelates of 2,2′‐Bidipyrrin: Stable Analogues of the Labile Iron Bilins

“…[26][27][28] A substitution of hydrogen atoms for any other group at these positions would directly enhance the intramolecular repulsion and, therefore, the lability in complexes of such tetrapyrroles. 2,2'-Bidipyrrin compounds have been explored before as nitrogen-containing ligands in a number of mono-and dinuclear transition-metal chelates, [17,20,22,24,25,29,30] and the propensity of the terminal positions for chemical transformations has occasionally been documented. [31][32][33][34] Stable iron chelates, such as 2, can indeed be obtained from these ligands (Scheme 1), and we report herein the preparation, structure, spectroscopic analysis, and biomimetic reactivity of a unique series of iron 2,2'-bidipyrrin complexes [FeX-A C H T U N G T R E N N U N G (bdp)] (X = F, Cl, Br, I).…”