Diverse Activation Modes in the Hydroboration of Aldehydes and Ketones with Germanium, Tin, and Lead Lewis Pairs

Abstract

Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: http://dx.

Synthesis of Norbornene-Based Phosphine-Stabilized Silylium Ions Behaving as Masked Frustrated Lewis Pairs

“…Dry and oxygen-free solvents were used. 1 H, 11 B, 13 C, 19 F, 28 Si and 31 P NMR spectra were recorded on Brucker Avance II 300 MHz, Avance III HD 400 MHz and Avance I and II 500 MHz spectrometers. 1 H, 29 Si and 13 C NMR chemical shifts are reported in parts per million (ppm) relative to Me4Si as internal standard.…”

“…11 B NMR downfield chemical are expressed in ppm relative to BF3.Et2O. 19 F-chemical shifts were reported in ppm relative to CFCl3 as an external standard. 31 P NMR chemical shifts are expressed in ppm relative to 85 % H3PO4.…”

“…11 B NMR (160 MHz, CD2Cl2): δ = -16.6 (s, BAr). 19 F NMR (471 MHz, CD2Cl2): δ = -132.5 (br,JFF = 20.5 Hz,JFF = 19.3 Hz,. 29 Si NMR (99 MHz, CD2Cl2): δ = 23.8 (d, 2 JSiP = 2.5 Hz, SiMe2), 23.8 (d, 2 JSiP = 2.7 Hz, SiMe2), -0.3 (d, 1 JSiP = 172.6 Hz, Si + ), -2.1 (d, 1 JSiP = 171.2 Hz, Si + ).…”

N-Heterocyclic Carbene-Stabilized Germa-acylium Ion: Reactivity and Utility in Catalytic CO2 Functionalizations

“…In recent years the transition metal like ability of germanium has been shown providing the first examples of low-valent main group dihydrogen activation and multiple bond catalysis. [32][33][34][35][36][37][38][39][40] With the latter example possible due to the ability of germanium to switch between its +2 and +4 oxidation states. With these incentives in mind, we targeted the synthesis of a Lewis base stabilized germanium oxide ion, the elusive heavier analog of an acylium ion, and to examine its application in CO 2 functionalization.…”

Catalytic hydroboration of carbonyl compounds and pyridine derivatives with the NHC-parent silyliumylidene cation

“…However, among the various single site main group catalysts for hydroboration, [47][48][49][54][55][56][57] there is only one report of a silicon based catalyst by Sen et al in 2017. 58 The amidinato-silane catalyst has been reported to selectively catalyse the hydroboration of aldehydes and aldimines to the corresponding borate esters and amine boronate esters, respectively, under mild reaction conditions (Scheme 4a).…”