Synthesis of a “Masked” Terminal Nickel(II) Sulfide by Reductive Deprotection and its Reaction with Nitrous Oxide

Abstract

Addition of 1 equiv of KSCPh3 to [LRNiCl] (LR = {(2,6-iPr2C6H3)NC(R)}2CH, R = Me, tBu) in C6H6 results in the formation of [LRNi(SCPh3)] (1, R = Me; 2, R = tBu) in good yields. Subsequent reduction of 1 and 2 with 2 equiv of KC8, in cold (-25 °C) Et2O, in the presence of 2 equiv of 18-crown-6, results in the formation of “masked” terminal NiII sulfides, [K(18-crown-6)][LRNi(S)] (3, R = Me; 4, R = tBu), also in good yields. An X-ray crystallographic analysis of these complexes suggests that they feature partial multiple bond character in their Ni-S linkages. Addition of N2O to a toluene solution of 4 provides [K(18-crown-6)][LtBuNi(SN=NO)] (6), which features the first example of a thiohyponitrite ([κ2-SN=NO]2-) ligand.

Trapping of an NiII Sulfide by a CoI Fulvene Complex

“…We recently reported the synthesis of an Ni II [23][24][25] resulting in our classification of this complex as a "masked" terminal sulfide. Importantly, however, the presence of the coordinating [K(18-crown-6)] + cation likely tempers the reactivity of the sulfide ligand, and possibly limits the extent of reactivity of this functional group.…”

“…The Ni-S and C-S bond lengths of 2.181(2) Å and 1.870(7) Å, respectively, are both consistent with single bonds. 23,26 For comparison, the Ni-S bond length in the starting material is markedly shorter (2.0869(1) Å). 23 The Ni-N bond lengths in 1 (1.901 (4) Figure S6), which is also consistent with the proposed mechanism.…”

“…23,26 For comparison, the Ni-S bond length in the starting material is markedly shorter (2.0869(1) Å). 23 The Ni-N bond lengths in 1 (1.901 (4) Figure S6), which is also consistent with the proposed mechanism. The solution phase redox properties of 1 were investigated by cyclic voltammetry.…”

Reactivity of a Nickel Sulfide with Carbon Monoxide and Nitric Oxide

“…These complexes have proven to react with a variety of small molecules, including CS 2 and N 2 O. 10,11 Given its potent reactivity, we hypothesized that…”

Aluminium‐Mediated Carbon Dioxide Reduction by an Isolated Monoalumoxane Anion

“…[35] Interestingly,t he direct addition of N 2 Ot o an isolated metal-oxo species has not been developed as as ynthetic route to this ligand. [36] In conclusion, we have demonstrated that the aluminyl anion [Al(NON Ar )] À reacts with two abundant greenhouse gases under mild conditions to generate innocuous and potentially useful chemical products.B oth reactions proceed through cycloaddition to an intermediate monoalumoxane anion, which has been isolated as the potassium salt. [36] In conclusion, we have demonstrated that the aluminyl anion [Al(NON Ar )] À reacts with two abundant greenhouse gases under mild conditions to generate innocuous and potentially useful chemical products.B oth reactions proceed through cycloaddition to an intermediate monoalumoxane anion, which has been isolated as the potassium salt.…”