Reversible P–P bond cleavage at an iridium(iii) metal centre

Abstract

We show that a simple, reversible, P–P bond cleavage/coupling transformation in a well-defined mononuclear Ir(κ1-R2P-PR2) complex is possible under ambient conditions.

Gradual Coordination and Reversible P–P Bond Activation of a P3‐Unit with Transition Metal Carbonyls

“…Remarkably this P–P bond activation is a reversible process and starting from the fully fragment P 1 ‐unit in which the phosphorus atom is exclusively coordinated to metal atoms, the initial P 3 ‐unit is regenerated with nucleophilic reagents such as methyllithium. The here reported reversible P–P bond activation complements previously published P–P bond activation processes, [ 16 ] by proceeding reversibly in a stereospecific manner and avoiding precious metals. Besides implications for the activation of P–P bonds and modifications of elemental phosphorus in which related chain‐like motifs can be found, we believe that the aspect of reversibility will spark new possibilities in the formation of homoatomic P‐chains in a defined and possibly catalytic manner, materials for which attractive properties have been forecasted which are difficult if not impossible to obtain otherwise.…”

The Backbone of Success of P,N-Hybrid Ligands: Some Recent Developments

“…Likewise the carborane functionalised phosphine 6k could be prepared from CH 2 O, H 2 NPh in DMF at 60 • C for 3 h and showed two singlets at 30.2 and 36.6 ppm (ratio 30:1 for rac:meso) for the two diastereomers [107]. Our group recently described a novel diphosphane 6l, based on two five membered, bicyclic P 2 C 2 N, rings that could be prepared from [P(CH 2 OH) 4 ] + and (4-Me 2 N)C 6 H 4 NH 2 or (4-MeO)C 6 H 4 NH 2 [108,109]. Microwave assisted Kabachnik-Fields reaction of aminomethylphosphine oxides and (CH 2 O) n and Ph 2 P(O)H gave the corresponding (un)symmetrical phosphine oxides, such as 6m, in excellent (>90%) yield bearing a central -NH-or -NR-group [110].…”