Kinetic‐Mechanistic and Solid‐State Study of the Oxidative Addition and Migratory Insertion of Iodomethane to [Rhodium(S,O‐BdiPT or N,O‐ox)(CO)(PR¹R²R³)] Complexes

Abstract

Rhodium(I) carbonyl complexes containing bidentate X, O-Bid [S,O-BdiPT or N,O-ox; S,O-BdiPTH = N-benzoyl-N′,N′-(diphenyl)thiourea; N,O-oxH = 8-hydroxyquinoline] ligands of the form [Rh(X,O-Bid)(CO)(PR 1 R 2 R 3 )] (R 1 , R 2 , R 3 = Ph or Cy) bearing different phosphine ligands, were investigated, the structural characterization of four example complexes is described and an extensive spectroscopic kinetic-mechanistic study of the oxidative addition of iodomethane thereto is discussed. Reaction with iodomethane led to Rh III -acyl species as secondary (final) products, whereas the primary Rh III -alkyl complexes, although rapidly formed, were only observed as intermediates, in small quantities for S,O-BdiPT (large S-Rh-O bite angle of 90-91°) but in significant amounts for N,O-ox complexes (less [a]

Crystal structure of carbonyl(2-methylquinolin-8-olato-κ2 N,O)(triphenylarsine-κAs)rhodium(I), C29H23AsNO2Rh

“…altering the electronic and steric properties of the ligand resulting in significant changes in the outcome of the catalytic process. These complexes have been studied intensively for potential application in catalytic hydroformylation, hydrogenation, carbonylation, and decarbonylation [8][9][10][11][12][13][14][15][16][17][18][19]. The coordination mode in the title complex is similar to the complexes reported previously [20].…”

The crystal structure of (E)-1-(quinolin-2-ylmethyl)-2-((1-(quinolin-2-ylmethyl)pyridin-2(1H)-ylidene)amino)pyridin-1-ium, C30H25BrN5

“…Pyridyl based type of ligands have contributed a great deal across many fields [9][10][11][12]. Subsequently, a great deal of interest towards multi-dentate pyridyl based ligands has grown over the decades across many disciplines including photoluminescence [13], medicinal chemistry [14], catalysis [15,16] and radiopharmaceutical [17] chemistry, also as pursued in our research group [18][19][20]. It is for this evidence that the tailoring of the multi-dentate ligands are still of paramount importance.…”

Redox Properties of Mononuclear Dicarbonyl and Carbonylphosphine Rhodium (I) Complexes Containing β-diketonate Ligands

“…татными β-дикетонатными лигандами являются эффективными гомогенными катализаторами гидроформилирования олефинов [1][2][3][4][5][6]. В их основе, как и в других каталитических процессах с участием родия (I) [7][8][9][10][11][12][13], лежит способность плоскоквадратных комплексов родия (I) к окислительному присоединению различных органических субстратов с образованием октаэдрических комплексов родия (III), а также к образованию вакантного координационного места за счет элиминирования одного из лигандов. В связи с этим в настоящее время все большее внимание уделяется изучению механизмов окисления с участием комплексов родия (I) и прогнозированию поведения этих соединений в каталитических редокс-реакциях с органическими субстратами в зависимости от их лигандного окружения [1][2][3][4][5][6][7][8][9][10][11][12][13].…”