Thionylimido Complexes

Abstract

An improved route to d‐block and main group NSO complexes is presented including the synthesis of the first antimony(V) complexes, (Ar3Sb(NSO)2), and copper examples [CuBipy(PPh3)NSO]. The structures of eight complexes are reported. The observed variation in M–N–S bond angles is due to the combination of orbital overlap (ligand‐to‐metal bonding) and the degree of ionicity of the bonding.

Bridging (Thionylimido)metal Complexes

“…The formation of this ring leads to minor changes from the structure of 1 , the most notable being contraction of the N–Ti–N angle from 96.0(1)° in 1 to 89.24(9)° in 2 and the increase of the Ti–N distance from 2.013(2) Å in 1 to an average of 2.0495(30) Å in 2 . The N–S–O angles in 2 are somewhat reduced at 116.49(13) and 116.82(13)° compared to those in 1 [119.1(2)°] and Pt­(PMe 3 ) 2 (NSO) 2 [123.3(8) and 121.4(8)°] .…”

“…We note that the [NSO] − anion can be considered as an isoelectronic analogue of SO 2 , which has diverse coordination chemistry, including acting as a bridging ligand . Following our recent work leading to a simplified route to thionylimido complexes, we decided to investigate the potential for forming bimetallic systems containing the NSO anion. There are a number of examples of bimetallic complexes containing titanium, − and together with the report of the use of Cp 2 Ti in the bimetallic [Cp 2 TiNi­(S 2 N 2 ) 2 ], this encouraged us to investigate syntheses using bis­(thionylimido)­titanocene as a scaffold to create heterobimetallic systems.…”