Catalytic Formation of Silicon–Heteroatom (N, P, O, S) Bonds

Abstract

Silicon and its compounds with other heteroatoms have received considerable attention, particularly because of their applicative ability. Silicon forms a large number of compounds with other p‐block elements (e.g., C, N, S, O, F, Cl, and others). All of them affect practical chemistry to some extent and are characterized by unique properties. This article highlights recent developments and covers the literature from the last 10 years. It is mainly focused on catalytic methods for silicon–nitrogen, silicon–phosphorus, silicon–oxygen, and silicon–sulfur bond formation. The scope and applications of these practical compounds will also be discussed.

Half-Sandwich Arene-Osmium(II) Complexes with Phosphinite Ligands

“…These compounds are of interest as they represent rare examples of tethered arene-ruthenium(II) complexes incorporating pendant phosphinite donors [2][3][4], a field largely dominated by the use of arene ligands featuring classical phosphines as the pendant donor group [1,5]. Moreover, we also demonstrated their utility as catalysts for the cross dehydrogenative coupling of hydrosilanes with alcohols [1], a process of relevance since it allows a simple access to useful alkoxysilane reagents [6,7], and with potential application in the field of hydrogen storage and production [8]. As shown in Scheme 1, the synthesis of complexes [RuCl 2 {η 6 :κ 1 (P)-C 6 H 5 (CH 2 ) n OPR 2 }] was accomplished in two steps involving the initial cleavage of the chloride bridges of [{RuCl(µ-Cl)(η 6 -arene)} 2 ] by the phosphinites, to generate the corresponding mononuclear adducts [RuCl 2 (η 6 -arene){R 2 PO(CH 2 ) n Ph}], and a subsequent intramolecular exchange of the coordinated arene under thermal conditions (120 • C) [1].…”

“…The Os(1)-P(1) and P(1)-O(1) bond distances (2.318(2) and 1.611(4) Å, respectively) are also comparable to those found in the structure of [OsCl2(η 6 -p-cymene)(PPh2OH)] (Os-P = 2.321(1) Å and P-O = 1.603(4) Å) [15]. (2); Os(1)-Cl(1) = 2.408(2); Os(1)-Cl(2) = 2.406(2); Os(1)-P(1) = 2.318(2); P(1)-O(1) = 1.611(4); P(1)-C(11) = 1.803(6); P(1)-C(17) = 1.823(6); Os(1)-C(23) = 1.448 (7); C*-Os(1)-P(1) = 127.47(4); C*-Os(1)-Cl(1) = 125.55(5); C*-Os(1)-Cl(2) = 127.96(4); Cl(1)-Os(1)-Cl(2) = 86.83 (7); Cl(1)-Os(1)-P(1) = 86.26 (6); Cl(2)-Os(1)-P(1) = 89.31(6); Os(1)-P(1)-O(1) = 114.0(2); Os(1)-P(1)-C(11) = 111.6(2); Os(1)-P(1)-C(17) = 124.2(2); Hydrogen atoms have been omitted for clarity. Thermal ellipsoids are drawn at the 20% probability level.…”

Chemoselective and Catalyst‐Free O‐Borylation of Silanols: A Facile Access to Borasiloxanes

“…The applications of silicon and boron derivatives in organic and inorganic chemistry are innumerable and their compounds containing bonds with other heteroatoms have received considerable attention, particularly as reagents in metal‐free reactions . The B‐O‐Si moiety is common in material chemistry, especially in the synthesis of poly(borosiloxane)s, which show unique and valuable properties, including high stability and heat resistance .…”

N‐Silylation of Amines Mediated by Et3SiH/KOtBu

“…In recent years, these methods are complemented by protocols based on a cross‐dehydrogenative coupling of hydrosilanes and amines, with H 2 being the exclusive by‐product of the catalytic process. In this regard, a comprehensive review of catalytic bond formation reactions for silicon−nitrogen (and other heteroatoms) has been published by Kuciński and Hreczycho in 2017 . Several catalytic processes have been developed over the years to obtain compounds containing the Si−N bond.…”