Template Synthesis of Chiral Vicinal Diphosphinites as Their Pt^II and Pd^II Complexes

Abstract

The metal-templated synthesis of a few examples of vicinal diphenylphosphinites is accomplished when the corresponding vicinal diols react with the diphenylchlorophosphane complexes cis-[MCl 2 (PPh 2 Cl) 2 ] (M = Pt, Pd) in anhydrous THF. This process is proposed as a new synthetic route for Pt II and Pd II complexes of the new ligands 1,2-bis(diphenylphosphinito)butane, 2,3-bis(diphenylphosphinito)butane, and 2,3-bis(diphenylphosphinito)diisopropyl-L-tartrate, containing seven-membered chelate rings including stereogenic

The application of tunable tridendate P‐based ligands for the Ru(II)‐catalysed transfer hydrogenation of various ketones

“…The progress of this reaction was conveniently followed using 31 P‐{ 1 H} NMR spectroscopy. The 31 P‐{ 1 H} NMR spectra of compounds 1 and 2 show single resonances due to AMPP at 111.10 ppm (s, OPPh 2 ) and 60.71 ppm (s, NPPh 2 ) and phosphinite at 113.93 ppm, respectively, in line with the values previously observed for similar compounds . Typical 31 P‐{ 1 H} NMR spectra of these ligands are illustrated in the supporting information (SI, spectra 1.1–1.4).…”

Gold(0) and Gold(III) Reactivity towards the Tetraphenyldithioimidodiphosphinic Acid, [Ph2P(S)NHP(S)Ph2]

“…It is worthy of note that the presence of strong intramolecular hydrogen bonds is not unusual in phosphane‐derived compounds. Some examples reported in the literature include complex 5 30 which features a (N−H ··· O − ) bridge, the chloro‐bridged platinum( III ) dimer [PtCl(Ph 2 PO) 2 H] 2 35 and [(Ph 2 PO) 2 H(Ph 3 PO)] + I 3 − in which an intramolecular hydrogen bond drives the cation conformation36a and the salts [(Ph 3 PO)H(Ph 3 PO)] + [AuCl 4 ] − 36b and [(Ph 3 PO)H(Ph 3 PO)] + [ICl 4 ] − 36c…”

On the key role of water in the allylic activation catalysed by Pd (II)bisphosphinite complexes

“…The reaction is best carried out in the presence of one equivalent of water but is in no way unique as it has been observed in other systems as well. 7 The catalyst system described here, results in considerably improved yields. Although chiral forms of the catalysts are readily accessible from the available chiral pool of alcohols, optical yields are disappointingly low.…”