Exclusively hydrogen-substituted arsanylboranes: The synthesis of the unprecedented Lewis base stabilized monomeric parent compound of the arsanylborane H2AsBH2⋅NMe3 was achieved in a one-pot reaction in high yield and purity. The analogous phosphanylborane was synthesized in a similar manner. A series of different reactions was performed on H2AsBH2⋅NMe3 to show its broad reactivity pattern.
Upon reacting P(4)S(3) with AgAl(hfip)(4) and AgAl(pftb)(4) [hfip = OC(H)(CF(3))(2); pftb = OC(CF(3))(3)], the compounds Ag(P(4)S(3))Al(hfip)(4) 1 and Ag(P(4)S(3))(2)(+)[Al(pftb)(4)](-) 2 formed in CS(2) (1) or CS(2)/CH(2)Cl(2) (2) solution. Compounds 1 and 2 were characterized by single-crystal X-ray structure determinations, Raman and solution NMR spectroscopy, and elemental analyses. One-dimensional chains of [Ag(P(4)S(3))(x)](infinity) (x = 1, 1; x = 2, 2) formed in the solid state with P(4)S(3) ligands that bridge through a 1,3-P,S, a 2,4-P,S, or a 3,4-P,P eta(1) coordination to the silver ions. Compound 2 with the least basic anion contains the first homoleptic metal(P(4)S(3)) complex. Compounds 1 and 2 also include the long sought sulfur coordination of P(4)S(3). Raman spectra of 1 and 2 were assigned on the basis of DFT calculations of related species. The influence of the silver coordination on the geometry of the P(4)S(3) cage is discussed, additionally aided by DFT calculations. Consequences for the frequently observed degradation of the cage are suggested. An experimental silver ion affinity scale based on the solid-state structures of several weak Lewis acid base adducts of type (L)AgAl(hfip)(4) is given. The affinity of the ligand L to the silver ion increases according to P(4) < CH(2)Cl(2) < P(4)S(3) < S(8) < 1,2-C(2)H(4)Cl(2) < toluene.
The halogenation of Lewis-acid/base-stabilised phosphanylboranes () and arsanylboranes () with CX4 (X=Cl, Br) leads selectively to the substitution of both protons at the pentel atom and the new compounds [(CO)5W(X2PBH2.NMe3)] (:X=Cl, :X=Br) and [(CO)5W(X2AsBH2.NMe3)] (:X=Cl, :X=Br), respectively, are obtained. The new products were comprehensively characterised by spectroscopic methods and by X-ray crystallography. While compounds and show an antiperiplanar arrangement of the Lewis acid (W(CO)5) and the Lewis base (NMe3) in the solid state, a synclinal arrangement in and , respectively, was observed. Computational calculations of the optimised antiperiplanar and synclinal geometries of the compounds and in the gas phase slightly favour the antiperiplanar arrangement of the Lewis acid and the Lewis base for both compounds.
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.