Beiträge zur Chemie des Phosphors, 81: 1,2,5,6‐Tetraphosphabicyclo[3.3.0]octan

Abstract

1,2-Bis(phosphino)ethan, H,PCH,CH,PH,(l), reagiert mit Phosphorhalogenverbindungen, wie X(R)P -P(R)X, RPX,, PX,, oder Brom zu dem bislang unbekannten bicyclischen di-sekundaren Phosphan 1,2,5,6-Tetraphosphabicyclo[3.3.O]octan (2). Die Konstitution von 2 wurde spektroskopisch und durch chemischen Ringabbau aufgeklart.Contributions to the Chemistry of Phosphorus, 81 1,2,5,6-Tetraphosphabicyclo[3.3.O]octane1,2-Bis(phosphino)ethane, H2PCHZCH,PH, (I), reacts with phosphorus halogen compounds such as X(R)P -P(R)X, RPX,, PX, or bromine to the hitherto unknown bicyclic di-secondary phosphane 1,2,5,6-tetraphosphabicyclo[3.3.0]octane (2). The structure of 2 was elucidated spectroscopically and by chemical ring degradation.

The Main Group Macrocycle [{(PCH2CH2PAlMe2)2}4]⋅4 [AlMe3]

“…While organo ± phosphorus ligands are ubiquitous in transition metal chemistry, the catenation of phosphorus atoms in organophosphanes and related polyphosphorus anions has drawn attention from inorganic and solid-state chemists. [15,16] To this end, we developed a catalyst for the dehydrocoupling of primary phosphanes to organopolyphosphanes. These disciplinary boundaries have been further eroded with the studies of phosphanide and phosphanediyl clusters reported by the research groups of Fenske [8±11] and Driess.…”

“…In targeting such systems we first sought a convenient route to organopolyphosphanes as previously known syntheses were arduous. [15,16] Recrystallization of 1 from hexane at À 35 8C afforded colorless X-ray quality crystals. [17] In a recent demonstration of such catalysis, we employed the catalyst precursor [(Cp* 2 ZrH 3 Li) 3 ] to produce the macrocyclic P 16 ring compound (C 6 H 4 P 2 ) 8 [Eq.…”

“…[15,16] Recrystallization of 1 from hexane at À 35 8C afforded colorless X-ray quality crystals. The 31 P{ 1 H} NMR spectrum of 1 consists of two resonances at d À 22.5 and À 65.4, each showing secondorder coupling.…”

“…These disciplinary boundaries have been further eroded with the studies of phosphanide and phosphanediyl clusters reported by the research groups of Fenske [8±11] and Driess. [15,16] To this end, we developed a catalyst for the dehydrocoupling of primary phosphanes to organopolyphosphanes. In targeting such systems we first sought a convenient route to organopolyphosphanes as previously known syntheses were arduous.…”

“…[12±14] While these systems employ phosphorus atoms to link metals in complex clusters, we have targeted systems in which chains of phosphorus atoms act as metal-linking units. [17] In a recent demonstration of such catalysis, we employed the catalyst precursor [(Cp* 2 ZrH 3 Li) 3 ] to produce the macrocyclic P 16 ring compound (C 6 H 4 P 2 ) 8 [Eq. [15,16] To this end, we developed a catalyst for the dehydrocoupling of primary phosphanes to organopolyphosphanes.…”