On the behaviour of biradicaloid [P(μ-NTer)]₂towards Lewis acids and bases

Abstract

The well-known diphosphadiazane-1,3-diyl [P(μ-NTer)]2 (Ter = 2,6-bis(2,4,6-trimethyl-phenyl)-phenyl) was treated with Lewis bases such as N-heterocyclic carbenes and Lewis acids e.g. gold(i) chloride complexes. In the reaction with the Lewis base, fragmentation of the P2N2 framework was observed, yielding a salt of the type [(NHC)2P](+)[(TerN)2P](-) in a clean reaction. The reaction of [P(μ-NTer)]2 with gold(i) chloride afforded 1 : 1 and 1 : 2 complexes. The dinuclear complex [(ClAu)2P(μ-NTer)2P] displays a bridging P atom between both gold centers, as has been observed for P based zwitterions.

Biradicaloid and Zwitterion Reactivity of Dicarbondiphosphide Stabilized with N‐Heterocyclic Carbenes

“…Furthermore, a natural bond orbital (NBO) analysis confirmed that there is still one lone pair on each phosphorus atom, but the σ 3 ‐P I center (natural population analysis (NPA) charge: +0.398) is more electron rich than the noncoordinated phosphorus center (NPA charge: +0.487), which makes it plausible that in every case the second Lewis acidic moiety is coordinated to the same P atom as the first. Related gold complexes of biradicaloid III (Scheme ) have been reported recently by Schulz et al., and group 6 complexes have been studied computationally by Frontera and Streubel . Similarly, when 1 b was treated with two equivalents of Cu I Cl, ( IPr ) 2 C 2 PP(CuCl) 2 ( 9 ) was isolated as a dark red solid.…”

“…Aside from biradical‐like reactivity, the dicarbondiphosphide compounds can also act as Lewis bases. In this case, they are better represented by the zwitterionic structure IVc (Scheme ; see Scheme for resonance structures) . Treatment of 1 a with an excess of borane in THF afforded the red zwitterionic borane adduct with two borane molecules bonded to one of the phosphorus atoms in [( IPr H ) 2 C 2 PP(BH 3 ) 2 ] ( 6 ), which was obtained in 84.1 % yield (Scheme ).…”

On the synergistic interaction of an ionic liquid and biopolymers in the synthesis of strontium niobate

“…Cellulose is a polymeric chain composed of β(1→4) linked D-glucose units [13]. Cellulose has been used previously as a morphological agent, with fibers [18] cubic-like particles [19] or rods [20] being observed when it is incorporated into syntheses.…”

“…Chitosan is a high molecular weight linear polymer of 2-acetamido-2-deoxy-d-glucopyranose units linked together by 1,4-glycosidic bonds, obtained by the deacetylation of chitin. Chitin originates in fungi and exoskeletons of insects and crustaceans [13]. The most relevant feature of chitosan is the possession of NH2 groups which might vary the reactivity and chemistry significantly when compared to other polysaccharides.…”

“…By judicious selection of the organic phase, laboratory-grown inorganic materials with structures such as nanocrystals, nanorods, nanoplatelets nanofibres or aerogels can be produced. [8][9][10][11][12] A great deal of work has gone into understanding and establishing the optimal conditions for the synthesis of metal oxides using polysaccharides [13], however, recent works using ionic liquids to chelate metal cations with the support of these organic compounds have opened up new synthetic pathways. An Ionic liquid (IL) is a mixture of long-chain cations and coordinating anions [14].…”