Comparison of Two Phosphinidenes Binding to Silicon(IV)dichloride as well as to Silylene

Abstract

The cyclic alkyl(amino) carbene (cAAC) anchored silylene with two phosphinidenes was isolated as (cAAC)Si{P(cAAC)} (3) at room temperature, which was synthesized from the reduction of (Cl)Si{P(cAAC)} (2) using 2 equiv of KC. Compound 2 resulted from the reaction of 2 equiv of (cAAC)PK (1) with 1 equiv of SiCl. Compounds 2 and 3 are the first examples where two terminal phosphinidenes are binding each to a silicon center characterized by single crystal X-ray structural analysis. Furthermore, the structure and bonding of compounds 2 and 3 have been investigated by theoretical methods for comparison.

Low‐Valent Group 14 NHC‐Stabilized Phosphinidenide ate Complexes and NHC‐Stabilized K/P‐Clusters

“…The cation in 7 consists of five potassium atoms coordinated by four NHC-stabilized phosphorus atoms, formingadistorted window-likes hape. The potassium atoms on the edges of the window are coordinated by two mesityl groups and two phosphorus atoms, whereas the central potassium atom, being coordinated by four phosphorus atoms, is in between tetrahedral and square-planar coordination[ P1-K1-P2 97.19 (5) (6) pm] are consistent with those in 5 and 6. Also, the chemical shift in the 31 PNMR spectrum (s, À43.4 ppm) is in the same range as those observedf or 5 and 6,w hich meanst hat the 31 PNMR spectroscopy is not very sensitive towards different coordinationn umbersa nd geometries here.…”

“…Since the group of Robinson synthesized the first “parent” N‐heterocyclic carbene (NHC) stabilized phosphinidene in 2010, these compounds, and especially the additional functionalization of them, have gained high popularity, which is evident by the uprising number of publications and review articles in recent years . NHC‐stabilized phosphinidenes that are substituted with organic substituents were published by Arduengo in 1997 .…”

“…Roesky and co‐workers recently introduced a pathway for the generation of a cAAC‐stabilized lithium phosphinidenide [(cAAC)PLi] (cAAC=cyclic alkyl amino carbene), which was used for the synthesis of a selection of main‐group‐substituted phosphinidenes (especially Group 14 and phosphorus) through salt‐elimination reactions . Furthermore, they used this precursor for the synthesis of a silylene binding only two phosphinidenide substituents as well as a cAAC ligand . In 2017, our group developed an alkali‐metal phosphinidenide stabilized by a saturated NHC ligand as a precursor for salt‐elimination reactions, which was successfully demonstrated by the synthesis of Group 13 (Al, Ga), 14 (Si, Sn), and 15 (P, As, Sb, Bi) substituted phosphinidenes .…”

Treatment of Silylene–Phosphinidene with Chalcogens Resulted Exclusively in the Formation of Silicon‐Bonded Chalcogens

“…Our group has synthesized a cyclic (alkyl)(amino)carbene (cAAC)‐anchored silylene–phosphinidene ( A , Scheme ) through a two‐step synthetic route starting from a heteroleptic silylene monochloride and a chlorophosphinidene . Recently we isolated a silylene, stabilized through two terminal phosphinidene ligands ( B , Scheme ) . Another interesting example of a silylene with a low‐coordinate phosphorus atom is the NHC‐stabilized phosphasilenylidene ( C , Scheme ) that was synthesized by Filippou and co‐workers .…”

“…[5] Recently we isolatedasilylene, stabilized through two terminal phosphinidene ligands( B, Scheme 2). [6] Another interesting example of as ilylene with a low-coordinate phosphorus atom is the NHC-stabilized phosphasilenylidene (C,S cheme 1) that was synthesized by Filippou and co-workers. [7] Furthermore, we reported cAAC-dichlorosilylene-stabilized phosphinidene ( Cy cAAC)SiCl 2 !PÀTip( D, Scheme 1) starting from Cy cAAC, HSiCl 3 ,a nd TipPCl 2 (Tip = 2,4,6-iPr 2 C 6 H 2 ).…”