Very Stable Phosphiranes

Abstract

Zero-valent platinum complexes as precursors for hydrosilylation catalysts have been prepared for the first time with the new BABAR-Phos ligands (the structure of one such complex is depicted). These rather stable phosphiranes can be obtained when the three-membered PC ring is incorporated into a polycyclic cage.

A Novel N,P,C Cage Complex Formed by Rearrangement of a Tricyclic Phosphirane Complex: On the Importance of Non‐covalent Interactions

“…Other synthetic strategies for P,C cage structures include cycloaddition reactions of phosphaalkynes with cyclobutadienes6 ( III ), thermolysis of 1,2,3‐tris(pentamethylcyclopentadienyl)cyclotriphosphene7 ( IV ) and reactions of triphosphabenzene with phosphenium salts8 ( V ). P,C cage structures containing other heteroatoms directly bound to phosphorus,9 such as oxygen10 and nitrogen,11 are also known. In contrast to P,C cages, for which ring expansions, rearrangements and coordination chemistry have been reported, related N,P,C systems have not been studied intensively due to a lack of facile synthetic protocols.…”

Cycloadducts of 1‐Alkyl‐1,2‐diphospholes with N‐Phenylmaleimide: Synthesis, Structure, Oxidation, and Thionation Reactions

“…5, the small sum of valence angles at the phosphorus atom ( P ), as well as reflected pyramidality should make them good π acceptors and promising ligands in transition metal catalyzed reactions where the reductive elimination step is rate determining. For example, aminosubstituted phosphiranes (BABAR-Phos, P ∼ 250 • ) [9] are surprisingly stable under oxidative conditions and demonstrate high activity in hydrosilylations [5] and hydroborations [10]. Phenylphosphatrioxaadamantanes are also very stable to air and water, and demonstrate very high hydroformylation catalytic activity of their Rh complexes [8].…”

“…Moreover, dry crystals of mixed valent P III , P V 1,7-diphosphanorbornenes (3, 4) are air stable for more than 2-3 days, which makes these (2a) P1-C3 1.854(2); P1-C4 1.885(2); P1-P2 2.192(8); P2-C26 1.847(2); P2-C1 1.904(2); C1-C2 1.541(3); C2-C3 1.359(3); C1-C7 1.583(3); C4-C7 1.535(3); C3-P1-C4 92.31(9); C3-P1-P2 87.72 (7); C4-P1-P2 91.97(6); C26-P2-C1 105.9(1); C26-P2-P1 102.6(7); C1-P2-P1 84.98(6); (2b) P1-C3 1.849(9); P1-C4 1.889(9); P1-P2 2.196(3); P2-C26 1.861(10); P2-C1 1.907(8); C1-C2 1.545(2); C2-C3 1.357(11); C1-C7 1.572(12); C4-C7 1.537(12); C3-P1-C4 93.50(4); C3-P1-P2 85.51(3); C4-P1-P2 92.66(3); C26-P2-C1 108.1(4); C26-P2-P1 103.80(3); C1-P2-P1 85.14 (3). (10); P2-C26 1.826(3); P2-C1 1.891(3); C1-C2 1.539(4); C2-C3 1.348(4); C1-C7 1.585(3); C4-C7 1.546(4); C3-P1-C4 96.70(12); C3-P1-P2 87.44(9); C4-P1-P2 86.23 (9). (4b) P1-C3 1.848(2); P1-C4 1.875(2); P1-P2 2.195(8); P2-C26 1.827(3); P2-C1 1.898(2); C1-C2 1.542(3); C2-C3 1.358(3); C1-C7 1.570(3); C4-C7 1.545(3); C3-P1-C4 93.96(10); C3-P1-P2 85.80 (7); C4-P1-P2 88.38 (7).…”

Platinum organometallic compounds: classification and analysis of crystallographic and structural data. Part I. Monomeric Pt(0) and partly of Pt(II) with PtC4, PtA3B and PtC2A2 chromophores

“…There are seven white derivatives (Chetcuti et al 1981a, Howard et al 1982, Chandra et al 1987, Beuter et al 1991, Hitchcock et al 1997, Liedtke et al 1999 in which each Pt(0) atom is fi ve-coordinated (PtC 4 P). In the derivatives from Chetcuti et al (1981a) and Howard et al (1982) , two bidentate (chelating) C donor atom ligands with PPh 3 (Howard et al 1982 ) or Pcy 3 (Chetcuti et al 1981a) form the PtC 4 P chromophore.…”

“…The three-membered C − Pt − C angles range from 36.1(4) ° to 41.9(4) ° (mean 38.6 ° ). In the remaining fi ve derivatives (Chandra et al 1987, Beuter et al 1991, Hitchcock et al 1997, Liedtke et al 1999, a tetradentate C donor ligand and a monodentate P donor ligand form the PtC 4 P chromophore.…”