Bis(tetraethylammonium) nickel tetrakisthiophenolate: a new polymorph

Proton‐Reduction Reaction Catalyzed by Homoleptic Nickel–bis‐1,2‐dithiolate Complexes: Experimental and Theoretical Mechanistic Investigations

“…More specifically, the delocalized nature of the dithiolate ligands is altered and the Ni−S bonds acquire a bonding nature resembling that of Ni–S thiolate analogs. This is reflected in bond lengths because the calculated Ni−S bonds for [ 2 (SH)] 2− (2.325–2.436 Å) are close to those of similar [Ni(SPh) 4 ] 2− species reported in the literature (2.293–2.331 Å) …”

Synthesis and Characterization of Square Planar Nickel(II)−Arylthiolate Complexes with the Biphenyl-2,2‘-dithiolate Ligand

“…The nickel−sulfur distances in 2 are similar to those in 1 but are longer than most mononuclear square planar Ni(II)−thiolate complexes (2.156−2.212 Å), ,,− which are frequently alkylthiolate-ligated or have bidentate arylthiolate ligands with planar constraints and/or five-membered chelate ring sizes (for example, benzene-1,2- dithiolate ligands). Mononuclear complexes with monodentate arylthiolate ligands typically display distorted tetrahedral structures. ,,− The S−Ni−S angles in 2 average to 90.03° with the smallest at 83.46° and the largest at 94.92°. The individual S−Ni−S angles in 2 deviate more from 90° than nearly all of the other square planar Ni II −tetrathiolate complexes it can be compared to. ,,− The interligand angles in 2 are smaller than the intraligand angles; a similar pattern is seen in 1 and probably reflects an influence of the bite angle of L .…”

“…Mononuclear complexes with monodentate arylthiolate ligands typically display distorted tetrahedral structures. 49,51,[61][62][63] The S-Ni-S angles in 2 average to 90.03°w ith the smallest at 83.46°and the largest at 94.92°. The individual S-Ni-S angles in 2 deviate more from 90°than nearly all of the other square planar Ni II -tetrathiolate complexes it can be compared to.…”

Tetrahedral and Square Planar Ni[(SPR2)2N]2 complexes, R = Ph & iPr Revisited: Experimental and Theoretical Analysis of Interconversion Pathways, Structural Preferences, and Spin Delocalization

“…Therefore, the Ni-S-P-N-P-S metallacycle adopts a twist conformation, and the metal core of 2 displays an ideal S 4 point group symmetry, with the main axis bisecting both endocyclic S-Ni-S angles. 25 Furthermore, the endocyclic S-Ni-S angles are slightly less than 109.5°(see Supporting Information, Table S3), thus the core of 2 exhibits a minor tetragonal elongation, in contrast to what has been found for most T d [M(SAr) 4 ] 2-complexes (M = Fe, 15,[51][52][53][54][55] Co, 15,16,51,52,[55][56][57][58][59] Ni [12][13][14][15][16][17][18] ) as well as the analogous M iPr,iPr L 2 complexes (M = Mn, 33 Co, 60 Zn 25 ), which are always compressed along the principal S 4 symmetry axis.…”

“…A search in the Cambridge Structural Database reveals that only a handful out of over 800 complexes bearing the Ni (II) S 4 core are not SP but instead display T d geometry. The mononuclear T d Ni (II) S 4 complexes, that have been structurally characterized up to date, can be divided into two groups: (i) Ni (II) complexes bearing monodentate arylthiolato ligands of the [Ni(SAr) 4 ] 2− general type, − and (ii) Ni (II) complexes bearing bidentate dithioimidodiphosphinato ligands, Ni[R 2 P(S)NP(S)R′ 2 ] 2 , R, R′ = aryl or alkyl (denoted as Ni R,R ′ L 2 ). The latter type of ligands are considered to be inorganic analogues of β-diketonates, and they readily form a wealth of M (II) L 2 coordination compounds, containing six-membered chelating rings, that exhibit extensive delocalization of π-electronic density among the S−P−N−P−S fragment. − Furthermore, their wide S···S “bite” range (ca .…”