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Versatility of Coordination Modes in Complexes of Monohydroxamic Acids with Half-Sandwich Type Ruthenium, Rhodium, Osmium and Iridium Cations

BuglyĂł, PĂ©ter

Parajdi-Losonczi, Péter László

BĂ©nyei, Attila Csaba

Lihi, Norbert

BĂ­rĂł, Linda

Farkas, Etelka

Wiley-VCH

2017

QD Chemistry / kémia

Complexation of the secondary N-methyl-acetohydroxamic acid (HMeaha) with [(eta(6)-p-cym)Ru(H2O)(3)](2+), [(eta(5)-Cp*)Rh(H2O)(3)](2+), [(eta(6)-p-cym)Os(H2O)(3)](2+) or [(eta(5)-Cp*)Ir(H2O)(3)](2+) cations and the primary acetohydroxamic acid (HAha) with the former two cations (first time in the literature) has been studied in aqueous solution using pH-potentiometry, NMR, ESI-MS and DFT calculations. Because the arene or arenyl ligands take three coordination sites of the metal ion, only three remain free for interaction with additional ligand(s). Meaha(-) forms five-membered hydroxamate type chelated [ML](+) and [M(OH)L], being the third coordination site occupied by a water molecule in the former complex and by a hydroxide ion in the latter one. While [ML](+) remains predominant even under basic conditions in the Ru- and Rh-containing systems, it is measurable only in slightly acidic region with the two 5d metal ions. Also the tendency for hydrolysis of the aqua ligand in [ML(H2O)](+) complexes follows the trend of the cations for hydrolysis, Os > Ir > Ru > Rh. The X-ray result did not show any role of the H substituent of Aha(-) in [((eta(5)-Cp*)Rh)(2)((2)-Aha)(2)](2+), in solution, however, its significant role was supported especially with Ru. All the results support the formation of a stable trinuclear [M3H-2L3(H2O)](+) species in which doubly deprotonated (hydroxymate type) ligands bridge two metal centres by coordinating via the two oxygens to the one cation and via the N-donor to another one.

angol

Article

PeerReviewed

info:eu-repo/semantics/article

text

http://real.mtak.hu/74332/1/ChemSelect_Buglyo_ms_v12.pdf

Buglyó, Péter and Parajdi-Losonczi, Péter László and Bényei, Attila Csaba and Lihi, Norbert and Bíró, Linda and Farkas, Etelka (2017) Versatility of Coordination Modes in Complexes of Monohydroxamic Acids with Half-Sandwich Type Ruthenium, Rhodium, Osmium and Iridium Cations. ChemistrySelect, 2 (26). pp. 8127-8136. ISSN 2365-6549

http://real.mtak.hu/74332/

https://doi.org/10.1002/slct.201701858

MTMT:3282802; doi:10.1002/slct.201701858