Phosphinine-based ligands: Recent developments in coordination chemistry and applications

Reactivity Studies of Phosphinines: The Selenation of Diphenyl-Phosphine Substituents and Formation of a Chelating Bis(Phosphinine) Palladium(II) Complex

“…The initial discovery of 2,4,6-triphenylphosphinine by Märkl [1] and the parent, unsubstituted phosphinine by Ashe [2] are now landmarks in low-coordinate main group chemistry and continue to inspire new research in the field [3,4]. Recent developments have focused on the use of phosphinines as ligands [5][6][7][8][9][10], particularly in homogeneous catalysis [11][12][13][14][15] where they show interesting differences to conventional phosphine ligands. Examples from our group include the use of phosphinophosphinine complexes as small bite-angle ligands [16] for Ru-catalysed transfer hydrogenation, alcohol upgrading and acceptorless dehydrogenation reactions [17,18] as well as Cr catalysts for ethylene oligomerisation reactions producing unusual alkyl-and alkenylcyclopentane products [19] and Rh complexes for the hydroboration of carbonyls [20].…”

“…Examples from our group include the use of phosphinophosphinine complexes as small bite-angle ligands [16] for Ru-catalysed transfer hydrogenation, alcohol upgrading and acceptorless dehydrogenation reactions [17,18] as well as Cr catalysts for ethylene oligomerisation reactions producing unusual alkyl-and alkenylcyclopentane products [19] and Rh complexes for the hydroboration of carbonyls [20]. Others researchers have demonstrated the exceptional behaviour of Rh-phosphinine complexes in hydroformylation [21,22] and hydrogenation reactions [23], Au-phosphinine catalysts for cycloisomerisations [24] and cyclometalated iridium(III)phosphinine precatalysts for water oxidation reactions [25] among many others [5,11].…”

“…Phosphinophosphinines are useful ligands for transition metal complexes [5,9] and form four-membered chelates that can be extended into five-membered chelates through oxidation of the phosphine with sulfur, which has been well-studied [10], or oxygen, selenium and organic azides [36], which are almost unknown. For example, phosphinines bearing two ortho-P(S)Ph 2 groups were cleanly synthesised from analogous diphenylphosphinesubstituted phosphinines by a reaction with elemental sulfur [37,38].…”

Silver‐Catalyzed Direct Regioselective C3 Phosphonation of 4H‐pyrido[1,2‐a]pyrimidin‐4‐ones With H‐phosphites

“…[1] In particular, organophosphorus compounds are often used as important intermediates and employed as synthesize ligands or organic catalysts in diverse chemical transformation. [2] Thus, much effort has been devoted to building CÀ P bonds. [3] During the last decades, metal catalysis, [4] photocatalysis, [5] electrochemeical catalysis, [6] and metal-free catalysis [7] for synthesis of organophosphorus compounds have been successfully developed.…”

A ruthenium cis-dihydride with 2-phosphinophosphinine ligands catalyses the acceptorless dehydrogenation of benzyl alcohol

“…the production of an amine-formate adduct, thus demonstrating facile CO 2 conversion. 40 The development of phosphinines, the phosphorus analogue of pyridine, as effective ligands for homogeneous catalysis has grown over the last 25 years, [41][42][43] and now includes applications such as Rh-catalysed hydroformylation 44 and hydrogenation, 45,46 Au-catalysed cycloisomerisations, 47 Cr-catalysed ethylene oligomerisation 48 and the hydroboration of carbonyls. 49 The application of homogeneous metal-phosphinine catalysts to confront energy challenges has also been explored, including in water oxidation reactions 50 and the catalytic upgrading of alcohols to advanced biofuels.…”