Skip to main content
eScholarship
Open Access Publications from the University of California

UC Santa Barbara

UC Santa Barbara Electronic Theses and Dissertations bannerUC Santa Barbara

Synthesis, Characterization, and Reactivity of "Masked" Terminal Nickel Sulfides

Abstract

Treatment of the Ni(II) chloride complexes, [LRNiIICl] (LR = {(2,6-iPr2C6H3)NC(R)}2CH, R = Me, tBu) with 1 equiv of KSCPh3 affords the Ni(II) triphenylmethylthiolate complexes, [LRNiII(SCPh3)], in good yields. The reaction of [LRNiII(SCPh3)] with 2 equiv of KC8 and L (L = 18-crown-6 or 2,2,2-cryptand) affords both [K(L)][LRNiII(S)] and [K(L)][CPh3] via reductive deprotection of the triphenylmethyl group. Treatment of [K(18-crown-6)][LtBuNiII(S)] with Ph2SiH2 affords a Ni(I) SH- complex, [K(18-crown-6)][LtBuNiI(SH)]. Treatment of [K(18-crown-6)][LtBuNiII(S)] with Me3SiOTf affords a Ni(II) trimethylsilanethiolato complex [LtBuNiII(SSiMe3)].

Treatment of [LtBuNiII(SCPh3)] with 2 equiv of decamethylcobaltocene (Cp*2Co) generates a transient NiII sulfide complex, [Cp*2Co][LtBuNiII(S)]. A subsequent deprotonation of [Cp*2Co]+ by [CPh3]- gives the CoI fulvenyl complex, [Cp*Co(C5Me4CH2)], which couples with the sulfide ligand in [Cp*2Co][LtBuNiII(S)] to form a Ni(I) cobaltocenium thiolate complex, [LtBuNiI(SCH2Me4C5)Co(Cp*)], concomitant with the reduction of the cobaltocenium cation.

Treatment of [K(18-crown-6)][LtBuNiII(S)] with CS2 yields the Ni(II) trithiocarbonate complex, [K(18-crown-6)][LtBuNiII(S,S:2-CS3)]. Treatment of [K(2,2,2-cryptand)][LtBuNiII(S)] with CS2 generates the double insertion product, a Ni(II) trithiocarbonate dithiocarboxylate complex, [K(2,2,2-cryptand)][(S,S:2-CS3)NiII{S,S:2-CS2(LtBu)}].

Treatment of [K(18-crown-6)][LtBuNiII(S)] with CO affords a Ni(II) carbonyl sulfide complex, [K(18-crown-6)][LtBuNiII(S,C:η2-SCO]. Treatment of [K(18-crown-6)][LtBuNiII(S)] with NO yields a nickel nitrosyl complex, [LtBuNi(NO)], and a perthionitrite salt, [K(18-crown-6)][SSNO].

Treatment of [K(18-crown-6)][LtBuNiII(S)] with N2O yields an unprecedented Ni(II) thiohyponitrite complex, [K(18-crown-6)][LtBuNiII(2-SNNO)]. Gentle thermolysis of [K(18-crown-6)][LtBuNiII(2-SNNO)] results in extrusion of N2 and formation of a thioperoxide complex, [K(18-crown-6)][LtBuNiII(2-SO)]. Treatment of [K(18-crown-6)][LtBuNiII(2-SO)] with CO, forms [K(18-crown-6)][LtBuNiII(S)] along with CO2, via O-atom abstraction. The Ni(II) sulfide then reacts with CO or CO2 to form [K(18-crown-6)][LtBuNiII(2-SCO)] and [K(18-crown-6)][LtBuNi(S,O:κ2-SCO2)], respectively. The thioperoxide complex, [K(18-crown-6)][LtBuNiII(2-SO)], can also react with the newly formed CO2 to form a putative monothiopercarbonate complex, [K(18-crown-6)][LtBuNiII(2-SOCO2)], which can then transfer an S atom to CO, forming COS and [K(18-crown-6)][LtBuNiII(2-CO3)].

Main Content
For improved accessibility of PDF content, download the file to your device.
Current View