Different cyclic (alkyl)(amino)carbenes (CAACs) were reacted with yellow arsenic. Several products [(CAAC‐n)2(μ,η1:1‐As2)] (n=1 (1), 4 (2)), [(CAAC‐2)3(μ3,η1:1:1‐As4)] (3) and [(CAAC‐3)4(μ4,η1:1:1:1‐ As8)] (6) were isolated due to the differing steric properties of CAAC‐1‐4. The products contain As2, As4 or As8 units and represent the first examples of CAACs‐substituted products of yellow arsenic. The reactivity of As4 was compared with the reactivities of P4 and the interpnictogen compound AsP3, which led to a series of phosphorus‐containing derivatives such as ([(CAAC‐3)3(μ3,η1:1:1‐P4)] (4) and [(CAAC‐3)4(μ4,η1:1:1:1‐P8)] (7)) and [(CAAC‐3)3(μ3,η1:1:1‐AsP3)] (5). The products were characterized by spectroscopic and crystallographic methods and DFT computations were performed to clarify their formation pathway.
The reactivity of yellow arsenic and the interpnictogen compound AsP3 towards low‐valent group 13 compounds was investigated. The reactions of [LAl] (1, L=[{N(C6H3iPr2‐2,6)C(Me)}2CH]−) with As4 and AsP3 lead to [(LAl)2(μ,η1:1:1:1‐E4)] (E4=As4 (3 b), AsP3 (3 c)) by insertion of two fragments [LAl] into two of the six E−E edges of the E4 tetrahedra. Furthermore, the reaction of [LGa] (2) with E4 afforded [LGa(η1:1‐E4)] (E4=As4 (4 b), AsP3 (4 c)). In these compounds, only one E−E bond of the E4 tetrahedra was cleaved. These compounds represent the first examples of the conversion of yellow arsenic and AsP3, respectively, with group 13 compounds. Furthermore, the reactivity of the gallium complexes towards unsaturated transition metal units or polypnictogen (En) ligand complexes was investigated. This leads to the heterobimetallic compounds [(LGa)(μ,η2:1:1‐P4)(LNi)] (5 a), [(Cp’’’Co)(μ,η4:1:1‐E4)(LGa)] (E=P (6 a), As (6 b), Cp’’’=η5‐C5H2tBu3) and [(Cp’’’Ni)(η3:1:1‐E3)(LGa)] (E=P (7 a), As (7 b)), which combine two different ligand systems in one complex (nacnac and Cp) as well as two different types of metals (main group and transition metals). The products were characterized by crystallographic and spectroscopic methods.
The nacnac Cu(I) compound [LCu(MeCN)] (2) (L = [{N-(C 6 H 3 Me 2 -2,6)C(Me)} 2 CH] − ) was reacted with complexes containing aromatic cyclo-E 5 ([Cp*Fe(η 5 -E 5 )], E = P (1a), As (1b), Cp* = η 5 -C 5 Me 5 ), cyclo-P 4 ([Cp‴Co(η 4 -P 4 )] (3), Cp‴ = η 5 -C 5 H 2 t Bu 3 ) and cyclo-E 3 ligands ([Cp‴Ni(η 3 -E 3 )], E = P (4a), As (4b)) yielding the heterometallic complexes [(Cp*Fe)(μ,η 5:2 -E 5 )(LCu)] (E = P (5a), As (5b)), [(Cp*Fe)(μ 3 ,η 5:2:1 -E 5 )(LCu) 2 ] (E = P (6a), As (6b)), [(Cp‴Co)(μ,η 4:2 -P 4 )(LCu)] ( 7), [(Cp‴Co)(μ 3 ,η 4:2:1 -P 4 )(LCu) 2 ] (8), and [(Cp‴Ni)(μ,η 3:2 -E 3 )(LCu)] (E = P (9a), As (9b)). These complexes are rare examples of the coordination of a group 11 metal to aromatic cyclo-E n (E = P, As; n = 3−5) ligands. All products were comprehensively characterized by crystallographic and spectroscopic methods. Their dynamic behavior in solution was studied by VT (variable-temperature) NMR spectroscopy, and their electronic structures were elucidated by DFT calculations.
Fe–Li–Pb heterotrimetallic triple-decker complexes were synthesized by reduction of pentaphospha- and pentarsaferrocene with the dilithioplumbole. Both complexes comprise bent P5/As5 middle decks and plumbole as lower decks.
The reactivity of white phosphorus and yellow arsenic towards two different nickel nacnac complexes is investigated. The nickel complexes [(L1Ni)2tol] (1, L1=[{N(C6H3iPr2‐2,6)C(Me)}2CH]−) and [K2][(L1Ni)2(μ,η1 : 1‐N2)] (6) were reacted with P4, As4 and the interpnictogen compound AsP3, respectively, yielding the homobimetallic complexes [(L1Ni)2(μ‐η2,κ1:η2,κ1‐E4)] (E=P (2 a), As (2 b), AsP3 (2 c)), [(L1Ni)2(μ,η3 : 3‐E3)] (E=P (3 a), As (3 b)) and [K@18‐c‐6(thf)2][L1Ni(η1 : 1‐E4)] (E=P (7 a), As (7 b)), respectively. Heating of 2 a, 2 b or 2 c also leads to the formation of 3 a or 3 b. Furthermore, the reactivity of these compounds towards reduction agents was investigated, leading to [K2][(L1Ni)2(μ,η2 : 2‐P4)] (4) and [K@18‐c‐6(thf)3][(L1Ni)2(μ,η3 : 3‐E3)] (E=P (5 a), As (5 b)), respectively. Compound 4 shows an unusual planarization of the initial Ni2P4‐prism. All products were comprehensively characterized by crystallographic and spectroscopic methods.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.