From As-Zincoarsasilene (LZn-As=SiL') to Arsaethynolato (As ≡C-O) and Arsaketenylido (O=C=As) Zinc Complexes.

From As-Zincoarsasilene (LZn-As=SiL') to Arsaethynolato (As≡C-O) and Arsaketenylido (O=C=As) Zinc Complexes.
Angew Chem Int Ed Engl. 2019 Jan 08;:
Authors: Driess M, Ballestero-Martínez E, Szilvási T, Hadlington T
Abstract
The reactivity of the As-zincosilaarsene LZn-As=SiL´ A (L = [CH(CMeNDipp)2], Dipp = 2,6-iPr2C6H3, L´ = [{C(H)N(2,6-iPr2-C6H3)}2]2-) towards small molecules has been investigated. Due to the pronounced zwitterionic character of the Si=As bond of A, it readily undergoes facile addition reactions with H2O and NH3, in forming LZnAs(H)SiOH(L´) 1 and LZnAs(H)SiNH2(L´) 2, respectively. Remarkably, oxygenation of A with N2O at -60 °C furnishes the deep blue 1,2-disiloxydiarsene, [LZnOSi(L´)As]2 4, presumably via dimerization of the arsinidene intermediate LZnOSi(L´)As 3. Instead, the oxygenation of A with CO2 leads to the monomeric arsaethynolato siloxido zinc complex LZnOSi(L´)(OC≡As) 5, essentially trapping the intermediary arsinidene 3 with liberated CO following initial oxidation of the Si=As bond. Density Functional Theory (DFT) calculations confirm the ambident coordination mode of the anionic [AsCO] ligand in solutions, with the O-arsaethynolato [As≡C-O] - in 5, and the As-arsaketenylido ligand mode [O=C=As]- present in LZnO-Si(L')(-As=C=O) 5' akin to the phosphorus analogous system, [PCO] -.
PMID: 30620428 [PubMed - as supplied by publisher]

Source: Angewandte Chemie - January 8, 2019 Category: Chemistry Authors: Driess M, Ballestero-Martínez E, Szilvási T, Hadlington T Tags: Angew Chem Int Ed Engl Source Type: research