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

Abstract

The 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)], which features the first example of a thiohyponitrite (κ2‐[SNNO]2−) ligand.

Synthesis and Mechanism of Formation of Hydride–Sulfide Complexes of Iron

“…42 Hayton made use of a thiolate as a S •− transfer agent to form novel uranium and nickel sulfide species. 43, 44 In each of these cases tritylthiolate was used, and the byproduct in these reactions was Gomberg’s dimer, the coupled product of two CPh 3 radicals. The observation of Gomberg’s dimer strongly suggests that these literature reactions proceeded through homolytic C-S bond cleavage, although detailed mechanistic studies were not performed.…”

Isolation of a Bimetallic Cobalt(III) Nitride and Examination of its Hydrogen Atom Abstraction Chemistry and Reactivity Towards H2

“…5 Of note, isolable compounds containing M=E or M≡E bonds have been dominated by the early to mid-transition metals, while the synthesis and isolation of late metal complexes presents a more significant challenge due to the progressive population of M=E/M≡E π*-orbitals, leading to high reactivity and instability. [6][7][8] In specific regard to Group 9 -11 metals in tetragonal ligand fields, it is considered the case that d-orbital occupation with electron counts of n ≥ 4 is incompatible with metal-ligand multiple bonds, a concept that has been coined the "oxo wall." 5,[9][10] Yet, the oxo wall can be circumvented through lowering the coordination number and symmetry, employing sterically encumbering ligands, 7,[11][12] and reducing the delectron count through metal oxidation.…”

“…[6][7][8] In specific regard to Group 9 -11 metals in tetragonal ligand fields, it is considered the case that d-orbital occupation with electron counts of n ≥ 4 is incompatible with metal-ligand multiple bonds, a concept that has been coined the "oxo wall." 5,[9][10] Yet, the oxo wall can be circumvented through lowering the coordination number and symmetry, employing sterically encumbering ligands, 7,[11][12] and reducing the delectron count through metal oxidation. 6,8,13 These strategies have been effective for a handful of Rh/Ir compounds such as the iridium(V)oxo Ir(O)(mes)3 (mes = mesityl) synthesized by Wilkinson, 14 and nitride species such as (PNP)Ir(N) (PNP = N(CHCHP t Bu2)2) reported by the groups of de Bruin and Schneider, 8 amongst others.…”

Unequivocal Characterization of an Osmium Complex with a Terminal Sulfide Ligand and Its Transformation into Hydrosulfide and Methylsulfide

“…The salt was obtained in low yield from the reaction crude resulting from the treatment of [N­( n -Bu) 4 ]­[Os­(N)­(CH 2 SiMe 3 ) 2 Cl 2 ] with Li 2 S. The crude containing mainly binuclear species . Like terminal oxo compounds, terminal sulfide complexes are frequent for iron and the transition elements found on the left side of Group 8, while they are very rare for the 3d metals on the right side and practically unknown for the platinum group metals . Some terminal sulfide derivatives of these elements have been proposed as transient species for the formation of condensed metal frameworks. , In two cases, the coordination of a terminal sulfur atom to a platinum group metal has been suggested, but they are controversial: the osmium salt mentioned above and a [Ru 2 Pd] cluster containing a Pd–S terminal bond .…”