Oxidation of tetraphosphacubane by bis(trimethylsilyl) peroxide, sulfur, and selenium [1]

Ma, Xiaohan; Birkel, M.; Wettling, Thomas; Regitz, Manfred

doi:10.1002/hc.520060104

Cited by 8 publications

(3 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The mean values of the Co-Co bond lengths are 2.53 for 1, 2.61 for 2a, and 2.64 Å for 2b with an increasing trend on going from the pristine complex 1 to the compounds with PX ligands (2a: X ‫ס‬ 0; 2b: X ‫ס‬ S). The six Co-P bond distances ( 4 (P 2 X 2 ) 2 ] (9), X ‫ס‬ S, Se [7], as well as to tetraphosphacubanes [8].…”

Section: Crystal and Molecular Structures Of The Doubleoxidized Complmentioning

confidence: 99%

PX (X = O, S, Se, Te) and P4Se as ligands in multinuclear CpR-cobalt complexes

1999

View full text Add to dashboard Cite

Section: Crystal and Molecular Structures Of The Doubleoxidized Complmentioning

confidence: 99%

PX (X = O, S, Se, Te) and P4Se as ligands in multinuclear CpR-cobalt complexes

1999

View full text Add to dashboard Cite

“…18 Achiral tetraphosphacubane has been successfully reacted with organic peroxides, sulfur, or selenium. One to four phosphorus atoms can be oxidized without opening the heterocubane structure 19 and P 4 -bishomoprismane and selena-P 4 -deltacyclene were selectively mono oxidized with sulfur or selenium. 20 This should be applicable to 5 as well.…”

mentioning

confidence: 99%

Optically active P₅-deltacyclenes: selective oxidation, ligand properties, and a diastereoselective rearrangement reaction

et al. 2016

View full text Add to dashboard Cite

a Cage-chiral tetra-tert-butyl-P 5 -deltacyclene 5 is accessible as a pair of highly enriched enantiomers 5'and 5''. The only secondary phosphorus atom P1 of the cage can be selectively oxidized by reaction with t-BuOOH. The P1-oxo species 9a' and 9a'', allow the direct determination of their ee values. Oxidation occurs with the complete retention of the optical activity of the compounds. The chiroptical properties of 9a' and 9a'' are strongly dominated by their cage chirality, the oxygen atom does not contribute significantly. Elemental sulfur and selenium oxidize P5 with high preference to yield P5-thio-and P5-seleno-P 5 -deltacyclenes 10 and 11 of the intact cages again. Longer reaction time and more than stoichiometric amounts of selenium, leads to tri-seleno-P 5 -tetracycloundecane 12, a partially opened oxidized rearrangement product. The ligand properties of racemic 9a were determined. Diphosphetane phosphorus atom P2 of 9a is the active donor center to bind a Cr(CO) 5 fragment, but a tautomerization of 9a takes place if [(benzene)RuCl 2 ] 2 is added. A hydrogen atom migrates from P1 to the oxygen atom to form a phosphinous acid ligand. The lone pair of P1 is regenerated and acts as the active ligand function of the cage in this case. As for 5, the base n-BuLi induces an efficient cage rearrangement reaction of 9a, where P1 and the neighboring carbon atom C4 containing its t-Bu substituent change places. C4 moves to its new position without breaking the bond with P5, this way forming the novel P1-oxo-P 5 -norsnoutene cage in a highly diastereoselective process.

show abstract

“…An improved synthetic method involves catalytic cyclooligomerization of the phosphaethyne in the presence of bis(cyclopentadienyl)zirconium chloride . The tetraoxide is prepared by oxidation of the tetraphosphacubane with bis(trimethylsilyl)peroxide and the tetrasulfide is synthesized by reaction with sulfur and triethylamine . The basicity of these compounds have been explored. , …”

mentioning

confidence: 99%

Remarkable Deprotonation Energies of Tetraphosphacubanes

Bachrach¹,

Gailbreath²

1998

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Oxidation of tetraphosphacubane by bis(trimethylsilyl) peroxide, sulfur, and selenium [1]

Abstract: ABSTRACT

Cited by 8 publications

References 22 publications

PX (X = O, S, Se, Te) and P4Se as ligands in multinuclear CpR-cobalt complexes

PX (X = O, S, Se, Te) and P4Se as ligands in multinuclear CpR-cobalt complexes

Optically active P₅-deltacyclenes: selective oxidation, ligand properties, and a diastereoselective rearrangement reaction

Remarkable Deprotonation Energies of Tetraphosphacubanes

Contact Info

Product

Resources

About

Oxidation of tetraphosphacubane by bis(trimethylsilyl) peroxide, sulfur, and selenium [1]

Abstract: ABSTRACT

Cited by 8 publications

References 22 publications

PX (X = O, S, Se, Te) and P4Se as ligands in multinuclear CpR-cobalt complexes

PX (X = O, S, Se, Te) and P4Se as ligands in multinuclear CpR-cobalt complexes

Optically active P5-deltacyclenes: selective oxidation, ligand properties, and a diastereoselective rearrangement reaction

Remarkable Deprotonation Energies of Tetraphosphacubanes

Contact Info

Product

Resources

About

Optically active P₅-deltacyclenes: selective oxidation, ligand properties, and a diastereoselective rearrangement reaction