BF3-Stabilized Metalated Sulfinylimides and Sulfurdiimides of the Type Cp(NO)2CrNSE·BF3 (E = O, NSiMe3)

Abstract

The coordination behavior of the imido derivatives of sulfur Me3SiNSE (E = O, NSiMe3) towards the 16‐electron complex [CpCr(NO)2]BF4 has been studied. In both cases coordination through an η1‐N linkage occurs as well as elimination of Me3SiF to afford the metalated derivatives Cp(NO)2CrNSE, which as N‐nucleophiles are additionally bound to the also‐formed electrophilic BF3 molecule (1, 2). Neither the possible addition products [Cp(NO)2Cr{N(SiMe3)SE}]BF4 as intermediates in the synthesis of 1, 2 nor the BF3‐free derivatives Cp(NO)2CrNSE as elimination products of 1, 2 could be stabilized or generated. The molecular structures of 1, 2 have been determined by single crystal X‐ray analyses. Both compounds contain a distorted tetrahedrally configured chromium center and an almost planar zig‐zag conformation of their sulfinyl imido (F3BNSO) and sulfur diimido ligand (F3BNSNSiMe3), respectively.

Reactions of Ruthenium Acetylide and Vinylidene Complexes Containing a 2-Pyridyl Group

“…The 1 H and 13 C signals of the Cp group at δ 5.00 and 91.4, respectively, confirm the formation of [Ru]-CO + . Perhaps trace moisture in the solution caused decomposition of the BF 4 − anion of complex 3a to form BF 3 , which then reacted with 3a to result in the formation of 5a and finally 6a . The methyl derivative 1b sequentially gave complexes 3b and 5b .…”

Bridging (Thionylimido)metal Complexes

“…2−4 (Thionylimido)metal complexes were first reported in the 1980s. 1 To date, there are no examples of [NSO] − bridging between transition-metal centers; there are reports of a chromium complex 6 where the [NSO] − anion coordinates to BF 3 as well as the metal and of Me 3 SiNSO coordinated to GaCl 3 . 5 In related work, there has been a report on the formation of bimetallic systems using the tetraimido [S(NtBu) 4 ] 2− anion (an analogue of sulfate).…”

“…Sulfur–nitrogen transition-metal complexes have attracted many investigations in the past, and while bridging sulfur–nitrogen ligands are not unknown, they are relatively uncommon; complexes containing naked anions displaying different bridging modes, via nitrogen, sulfur, or both, have been reported. − (Thionylimido)metal complexes were first reported in the 1980s . To date, there are no examples of [NSO] − bridging between transition-metal centers; there are reports of a chromium complex where the [NSO] − anion coordinates to BF 3 as well as the metal and of Me 3 SiNSO coordinated to GaCl 3 . In related work, there has been a report on the formation of bimetallic systems using the tetraimido [S­(N t Bu) 4 ] 2– anion (an analogue of sulfate) .…”

Thionylimido Complexes

“…A few transition metal complexes of the thionylimido (or as it could be called, thiazate) ligand have been reported, [5][6][7][8][9][10][11][12] from reactions such as that of metal halides with Me 3 SiNSO, or KNSO, or of thionyl chloride in liquid ammonia. [5][6][7][8][9][10][11][12] There is one example [13] of a coordinated NSO ligand stabilized by a BF 3 group in Cp(NO) 2 Cr(NSO).BF 3 , and recently there has been renewed interest in the area with the isolation of the iminosulfonium ion [Me 3 Si-N=S-O-SiMe 3 ] + , a potential source of [NSO] + , as well as other adducts of RNSO (R = H and Me 3 Si) with Lewis acids. [14] Herein we describe a simplified route to M-NSO complexes including the first examples of antimony(V), and copper complexes of the thionylimido ligand (compounds 5, and 6, 7 and 8 respectively).…”