Fixation and Release of Intact E₄ Tetrahedra (E=P, As)

Abstract

By the reaction of [NacnacCuCH3CN] with white phosphorus (P4) and yellow arsenic (As4), the stabilization and enclosure of the intact E4 tetrahedra are realized and the disubstituted complexes [(NacnacCu)2(μ,η(2:2)-E4)] (1 a: E=P, 1 b: E=As) are formed. The mono-substituted complex [NacnacCu(η(2)-P4)] (2), was detected by the exchange reaction of 1 a with P4 and was only isolated using low-temperature work-up. All products were comprehensively spectroscopically and crystallographically characterized. The bonding situation in the products as intact E4 units (E=P, As) was confirmed by theory and was experimentally proven by the pyridine promoted release of the bridging E4 tetrahedra in 1.

Coordination Behavior of [Cp′′2Zr(η1:1‐P4)] towards Different Lewis Acids

“…[6] Our group was also able to synthesize as eries of intact P 4 containingc omplexes such as [M(CO) 3 (PR 3 ) 2 (h 1 -P 4 )] (B;M= Mo, R = Cy;M = W, R = Cy, iPr) [7] and [Cp BIG Mn(CO) 2 (h 1 -P 4 )] (C;C p BIG = C 5 (4-nBuC 6 H 4 ) 5 ). [10] Interestingly,t he cationic class of complexes [Ag(h 2 -E 4 ) 2 ][pftb]( F;E = P, As;[ pftb] À = [Al{OC(CF 3 ) 3 } 4 ] À ), which the Krossing group synthesized for P 4 , [11] and our group for the correspondingA s 4 complex, [12] shows ap otential to transfer the intact E 4 unit to other metal fragments [12,13] or to release them to give, for example, metastables olutions of yellow arsenic. [9] For side-onc oordinated intact P 4 ,w ehave recently reported on the complex [LCu(h 2 -P 4 )] (E;L = [{N(C 6 H 3 iPr 2 -2,6)C(Me)} 2 CH]).…”

Molecular Pnictogen Activation by Rare Earth and Actinide Complexes

“…Reaction of the thorium butadiene complex (η In contrast, activation of molecular arsenic by homogeneous transition metal complexes is considerably more diverse; formation of cyclo-Asn ligands (n = 3-6, 8) [54,148], metal arsenic clusters [149], coordination of intact As4 tetrahedra to metal ions [133,150,151], fragmentation into As2 and other As4 ligands [152][153][154], catenation to As10 and As12 ligands [155], reactions to form PnAsm ligands [156], and full As4 fragmentation resulting in terminal M≡As arsenide bonds [157] have all been reported.…”

Facile storage and release of white phosphorus and yellow arsenic

“…Moreover, together with other coinage metal P 4 complexes, the air-sensitive silver(I) salts [Ag(η 2 -E 4 ) 2 ][pftb] (E = P, As; pftb = [Al{OC(CF 3 ) 3 } 4 ]) show to be suitable sources of intact E 4 (E = P, As) for particular chemical reactions, however with a limited scope due to the need of initial AgCl elimination 11–14 . Recently, we found two other systems, [(LCu) 2 (μ,η 2:2 -E 4 )] (E = P, As; L  = [{N(C 6 H 3 i Pr 2 -2,6)C(Me)} 2 CH − ]) and Cp R E 4 (E = P; Cp R  = Cp* (η 5 -C 5 Me 5 ), Cp″′ (η 5 -C 5 H 3 t Bu 2 ), Cp 4 i Pr (η 5 -C 5 H i Pr 4 ), Cp BIG (η 5 -C 5 (4- n BuC 6 H 4 ) 5 ); E = As, Cp R  = Cp PEt (η 5 -C 5 (4-EtC 6 H 4 ) 5 )), which coordinate either side-on the intact E 4 tetrahedra or radically opened an E–E bond to form a twofold organic-substituted compound with a tetraphospha/tetraarsabicyclo[1.1.0]butane as a central structural motif 15–17 . For both systems, we could show the release of intact E 4 tetrahedra, irreversible in solution, but reversible in the solid state for the latter case (except for E = As).…”