Electronic structure and photoelectron spectroscopy of d8 rhodium indenyl complexes

(1,2,3,4,7-Pentamethylindenyl)rhodium complexes with arene ligands

“…Comparing pairs of Cp/Cp * and C 9 H 7 / C 9 H 2 Me 5 complexes, one can notice that the decrease of donation from benzene (6-electron ligand) is connected with increase of donor properties of 5-electron ligand, in accordance with trans-effect. Further comparison of Cp/ C 9 H 7 and Cp * /C 9 H 2 Me 5 complexes allows to conclude that the indenyl ligands in the Rh(III) complexes studied are better donors than the cyclopentadienyls, similar to Rh(I) derivatives [9,10,33].…”

“…The related arene complexes of the (indenyl)rhodium fragment are presently unknown, in spite of rather well study of chemistry of this fragment [7][8][9][10]. Herein, we report the synthesis of (1,2,3,4,7-pentamethylindenyl)rhodium arene complexes [(g 5 -C 9 H 2 Me 5 )Rh(arene)] 2+ as well as the results of their structural and electrochemical study.…”

Synthesis and molecular structures of zirconium and hafnium complexes bearing dimethylsilandiyl-bis-2,4,6-trimethylindenyl and dimethylsilandiyl-bis-2-methyl-4,6-diisopropylindenyl ligands

“…The respective arylvinylketones can be prepared by acylation of the arene by acryloyl chloride or other acrylic acid derivative. In the presence of excess of AlCl 3 electron rich arenes give the respective indanones via one-pot acylation-cyclization reaction [4,14,15] as shown in Scheme 4. We used this approach for the synthesis of the desired trialkylindenes.…”

Photocatalytic properties of new cyclopentadienyl and indenyl rhodium(I) carbonyl complexes with water-soluble 1,3,5-triaza-7-phosphaadamantane (PTA) and tris(2-cyanoethyl)phosphine

“…On the one hand, the CO stretching frequencies in the cyclopentadienyl complexes are lower than those in the indenyl compounds because of less efficient MeCO back-bonding in indenyl complexes than in cyclopentadienyl compounds [21]. On the other hand, since all these complexes contain the same R ligand (R ¼ cp, ind), the differences found in the CO stretching vibration must derive from the different effects of the phosphine ligands.…”

“…This has been attributed to the flexibility of indenyl ligand to undergo facile h 5 eh 3 coordinative isomerizations known as the indenyl effect [21]. All the products were isolated as microcrystalline solids in 52e75% yields, based on [Rh(h 5 -R)(CO) 2 ] (R ¼ cp, ind), and characterized by IR and 1 H, 31 P, 13 C NMR spectroscopies, FAB þ -MS and elemental analyses.…”