Investigation of binap-based hydroxyphosphine arene–ruthenium(ii) complexes as catalysts for nitrile hydration

Anionic phosph(in)ito (“phosphoryl”) ligands: Non-classical “actor” phosphane-type ligands in coordination chemistry

“…Lately, bidentate mono O−anionic  1 -P(III)−phosph(in)ite complexes have been involved in a large number of catalytic transformations [176,177,[200][201][202][203][204][205][206].…”

Secondary Phosphine Oxides: Bifunctional Ligands in Catalysis

“…Soon thereafter, a potential intermediate for Ru-SPO catalyzed nitrile hydration was proposed by the same group for a different ligand system, 34, a complex synthesized by Pregosin via PÀ C cleavage of BINAP by water (Scheme 16). [85,86] Both, 34 and the putative Parkins' intermediate 35, also isolated by Pregosin, function as catalysts, albeit 35 at lower rates. In addition, 35 was shown to hydrolyze to give the amide product.…”

Unmasking the Action of Phosphinous Acid Ligands in Nitrile Hydration Reactions Catalyzed by Arene–Ruthenium(II) Complexes

“…[10] Similarly,c ompounds 3b [11] and 4d [14] are knownc ompounds.T he rest of complexes were fully characterized by meanso fe lemental analysis andI Ra nd multinuclear NMR spectroscopy; the data obtainedw erei nc omplete accordance with the proposed formulations (details are given in the Experimental Section). [15,16] Notably,a lthough the OH signal could only be observed in the 1 HNMR spectrum of 6b (a broad singlet at d = 6.68 ppm), the presence of this group was evidenced in all cases by the appearance of acharacteristic absorption band at ñ = 3063-3400 cm À1 in the IR spectra.…”

“…Startingf rom C,t he key metallacyclic species D could be isolated, and it proved to be catalytically active,a lthoughi ts effectiveness was lower than that of C under identical reaction conditions. [11] Aiming to unravel this intriguing mechanistic issue, we decided to explore in more detail the role played by the PÀOH-functionalized ligandsi nt he catalytic hydration of nitriles. To this end, ad iverse family of arene-ruthenium(II)c omplexes with this type of ligand, that is, compounds [RuCl 2 (h 6 -arene)(PR 2 OH)] (R = Me, Ph;a rene = C 6 H 6 , pcymene, 1,3,5-C 6 H 3 Me 3 ,C 6 Me 6 ) and [RuCl 2 (h 6 -arene){P(OR) 2 OH}] (R = Me, Et, Ph;a rene = C 6 H 6 , p-cymene, 1,3,5-C 6 H 3 Me 3 ,C 6 Me 6 ), which featured different steric and electronic properties, were synthesized and their catalytic behavior in the hydration of two model nitriles, namely,b enzonitrile and acetonitrile, was explored.…”

“…Notably, this alternative mechanism, which was not considered by Tyler and co‐workers,10 proved to be in competition with the more classical intermolecular water attack one in a recent work published by some of us and involving the tethered arene–ruthenium(II) complex C (Figure 2). Starting from C , the key metallacyclic species D could be isolated, and it proved to be catalytically active, although its effectiveness was lower than that of C under identical reaction conditions 11…”