Aromatic Diosmatricyclic Nitrogen-Containing Compounds

Osmabenzenes from Osmacycles Containing an η2‐Coordinated Olefin

“…[1][2] In particular, metallabenzenes, as one class of six-membered metallacyclic aromatic compounds derived from formal replacement of one CH moiety in benzene by an isolobal transition-metal fragment, have attracted considerable attention in recent years. [3][4] Several approaches have been developed to construct stable metallabenzene rings.…”

Formation and Rearrangement of Reduced Diiminepyridine Complexes of Zr and Hf

“…Suspended solid was removed by passing the liquid through Celite, and the solvent was removed in vacuo; 0.058 g (61 %) of a purple-brown solid residue was collected. C 31…”

“…An unexpected ligand isomerization to an amido/enamido form was observed for [( Et DIP)ZrCl 2 ], [( Et DIP)-HfMe 2 ] and [( Et DIP)TiMe 2 ], and a mechanism is proposed based on DFT calculations. less attention, although complexes with many heavier metals have been reported: La and Nd, [10,13] Zr, [14] U, [5,6,[15][16][17][18][19][20] Mo, [21,22] Re, [23] Ru, [24][25][26][27][28][29][30] Os, [31] Rh [30,[32][33][34] and Pd. [35] Non-innocence of the DIP ligand is an issue also with these heavier elements, although -judging from the literature -there is a higher tendency with these metals to engage in 2etransfer (or classical backdonation) rather than metal-to-ligand single electron transfer.…”

Testing the effectiveness of the isoelectronic substitution principle through the transformation of aromatic osmathiophene derivatives into their inorganic analogues

“…[20][21][22][23][24][25][26] The aim of the present work is to evaluate, in an extreme situation, the validity of the concepts mentioned in the preceding paragraphs, in order to design new stable molecules. The chosen system to achieve this goal is [OsCl2(SC3H3)(PH3)2] + ,which presents some characteristics that make it suitable for this purpose: 1) it is a simplified model of the osmabicycles (aromatic compounds where one Os atom is present in five-membered metallacycles), studied both experimentally and theoretically by Esteruelas et al, 27 2) this system was classified as clearly aromatic, 28 with participation of Os-d-orbital (especially dxz and dyz orbitals) closing the circuit of π-orbitals and allowing electronic delocalization on the planar OsC3S fragment. 29 Additionally, the presence of an Os-S bond is another interesting aspect, even though S has almost the same electronegativity that C, it is nearly double the size of its covalent radius and it has an extra lone pair of electrons (this is expected to play an important role in electronic delocalization after performing the IS procedure).…”