Oxidative Addition of Diethylchalcogenanes to Lappert's Germylene and Stannylene

Abstract

Oxidative addition of diethyldichalcogenanes Et 2 E 2 (E = S, Se, Te) to bis[bis(trimethylsilyl]amido]germylene and -stannylene M[N(SiMe 3 ) 2 ] 2 (M = Ge, Sn) proceed with formation of the corresponding bis(ethylchalcogenato)797 S (1), Se (2), Te (3)] and -stannanes (Me 3 Si) 2 N) 2 Sn(EEt) 2 [E = S (4), Se (5), Te (6)]. The solid state structures of 1-6 were determined by single-crystal X-ray diffraction.

Oxidative Addition to SnII Guanidinate Complexes: Precursors to Tin(II) Chalcogenide Nanocrystals

“…Perhaps not unsurprisingly, the average Sn–E bond length increase with the increasing atomic number of the chaclogen atom, and are in good agreement with both comparable Sn–E single bonds within the Cambridge Structural Database (CSD), specifically the related aryl and alkyl‐halcogenane compounds such as [{(Me 3 Si) 2 N} 2 Sn(E‐Ph) 2 ][7d] and [{(Me 3 Si) 2 N} 2 Sn(E‐Et) 2 ] as well as theoretical values for single bonds calculated from the sum of the single bond covalent radii…”

“…Perhaps not unsurprisingly, the average Sn-E bond length increase with the increasing atomic number of the chaclogen atom, and are in good agreement with both comparable Sn-E single bonds within the Cambridge Structural Database (CSD), specifically the related aryl and alkyl-halcogenane compounds such as [{(Me 3 Si) 2 [16] as well as theoretical values for single bonds calculated from the sum of the single bond covalent radii. [17] Despite the increase in steric demands of the {E-Ph} groups in 2-4 respectively, which is reflected in the lengthening of the Sn-E bonds, there is no accompanying change in the {E-Sn-E} angle (θ) or the interplanar {N 2 Sn}/{SnN 2 } angles (ψ) [15b] (see Table 2, interplanar angles observed for 1 [108.25°]).…”

“…The synthesis for the bis‐phenyl chalcogenide complexes 2–4 involves the straight forward reaction of the easily prepared stannylene 1 , with commercially available diphenyl dichalcogenides Ph 2 E 2 (E = S, Se and Te). The molecular structures of all three complex [{Me 2 NC(NCy) 2 } 2 Sn 2 ] (E = S ( 2 ), Se ( 3 ) or Te ( 4 )) have been determined by single‐crystal X‐ray diffraction experiments, revealing a family of isoreticular complexes, all of which poses a distorted pseudo octahedral geometry about the central Sn IV centre. As part of our study, we wished to access an alternative synthetic pathway to the mono‐chalcogen complexes of the general form [{Me 2 NC(NCy) 2 } 2 Sn = E] (E = S, Se or Te).…”

The Redox Properties of Germylenes Stabilized by N‐Donor Ligands

“…Physicochemical properties of 1 were studied by a number of methods, including UV/Vis [20] and photoelectron spectroscopy [21] . Moreover, some reactions of oxidative addition of 1 , in particular to dichalcogenanes (Scheme 5), were shown synthetically [22] . In addition, it was reported the reduction of an analogue of 1 having carbon substituents at the germanium center instead of nitrogen ones with sodium in THF [23] …”

Intramolecularly-stabilized Group 14 Alkoxides - Promising Precursors for the Synthesis of Group 14-Chalcogenides by Hot-Injection Method

“…Recently, we reported on the synthesis of highly stoichiometric, crystalline GeTe nanoparticles by reaction of GeCl 2 (dioxane) with Te(SiEt 3 ) 2 . Unfortunately, the low vapor pressure of GeCl 2 (dioxane) hampers its use as precursor in gas‐phase based processes, which is also true for crystalline single source precursors such as [(Me 3 Si) 2 N] 2 Ge( ER ) 2 ( E = S, Se, Te), Me 2 Si(N t Bu) 2 Ge( ER ) 2 ( E = S, Se), and [(Me 3 Si) 2 N] 2 Sn( ER ) 2 ( E = S, Se, Te), which have been recently applied in the wet chemical synthesis of group 14 chalcogenides . Our interest in volatile, ideally liquid precursors therefore prompted us to investigate group 14 aminoalkoxides, which may form intermolecularly base‐stabilized monomeric compounds.…”