The Construction of (N₂S₂)Ni−Pd Clusters: A Slant‐Chair, a Basket and a C₄‐Paddlewheel Structure

Abstract

In pursuit of an analogy between bidentate diphosphane ligands and cis-dithiolato nickel complexes, the easily prepared [bis(mercaptoethane)diazacycloheptane]nickel complex, Ni-1Ј, has been treated with Pd II and Ni II sources. With the latter, trinickel species are observed with typical slantchair structures; for palladium(ii) chloride, a basket-type structure is realized in which the floor of the basket is a PdS 4 unit and the sides are N 2 S 2 units. One chloride atom is held

Nickel(II)‐Mediated Reversible Thiolate/Disulfide Conversion as a Mimic for a Key Step of the Catalytic Cycle of Methyl‐Coenzyme M Reductase

“…One Ni is coordinated to two L SÀ which is bridged via its thiolato-S donors to another Ni that is ligated to four Ndonors of aL S-S ligand. Theavg.Ni ÀNand NiÀS thiol distances for the former Ni (Ni1 in Figure 1, middle) are 2.063(5) and 2.3992( 14) and those for the latter Ni (Ni2 in Figure 1, middle) are 2.100(4) and 2.4317( 14) ,respectively.T he SÀSdistance of Ni-uncoordinated disulfide of L S-S is 2.064(2) which is 0.02 shorter than that of the h 1coordinated disulfide of L S-S present in 1 Cl .T he NiÀS thiol distances found in 2 are comparable to those of the other reported hexa-coordinated Ni II -thiolate complexes [22,27,28] and to that of the MCR ox1-silent structure; [25] the latter revealed as an octahedral Ni II complex with aN 4 SO donor set and an avg. NiÀN F430 distance of 2.085 and NiÀS CoM and NiÀO Gln distances of 2.4 and 2.3 ,respectively.…”

“…One Ni is coordinated to two L SÀ which is bridged via its thiolato-S donors to another Ni that is ligated to four Ndonors of aL S-S ligand. Theavg.Ni ÀNand NiÀS thiol distances for the former Ni (Ni1 in Figure 1, middle) are 2.063(5) and 2.3992 (14) and those for the latter Ni (Ni2 in Figure 1, middle) are 2.100(4) and 2.4317 14,respectively.T he SÀSdistance of Ni-uncoordinated disulfide of L S-S is 2.064(2) which is 0.02 shorter than that of the h 1coordinated disulfide of L S-S present in 1 Cl .T he NiÀS thiol distances found in 2 are comparable to those of the other reported hexa-coordinated Ni II -thiolate complexes [22,27,28] and to that of the MCR ox1-silent structure; [25] Figure S15A) reveals as harp and intense stretch at 1734 cm À1 corresponding to the n CO of CH 3 CO 2 Et solvate in the structure.The n S-S stretch is absent, unlike in 1 Cl , 1 Solv and 2 where the n S-S stretch at % 475 cm À1 ( Figure S26) is observed. Theelectronic absorption spectrum of the greenish brown DMF solution of 3 ( Figure S15B) displays bands at l max /nm (e/m À1 cm À1 ) = 967 (975), 750 (1305), 580 (9350) and 304 (66 714).…”

“…Tw oL SÀ ligands are ligated to one octahedral Ni II in am eridional fashion with two thiol Sa nd two imine Nd onors of two ligands in cis and trans positions, respectively (Figure 1, bottom). Theo ther Ni is ligated to three donors of one L SÀ and is bridged via one thiol-S of aL SÀ ligated to first Ni thus adopts as quare planar coordination geometry.T he avg.N i À Na nd Ni À Sd istances found for the octahedral Ni II are 2.064(8) and 2.402(3) ,respectively,and the corresponding distances for the square planar Ni II are 1.902(8) and 2.177(3) ,r espectively.T hese Ni II ÀSd istances are comparable to those of the six [22,27,28] and four-coordinate [19,20,29] Ni II -thiolate complexes with N,Sdonor ligands.…”

Selective Electrocatalytic Reduction of Nitrogen to Hydrazine Using a Trinuclear Nickel Complex

“…These crystals were filtered, washed with cold water and dried in vacuum. 41 Alternatively, the structure of the Ni3S8 is boat-shaped due to the H-bonds between the terminal thiolates from the two different arms with the water molecules observed crystallographically ( Figure 2).…”

Nickel Thiolate Complexes as Ligands for Copper and Zinc: Novel Additions to a Library of Binding Modes

“…A wealth of structures has become available, and a range of possible bridging modes for the thiolate sulfur atoms have been reported. [7] The two cis-thiolate sulfur atoms in the parent nickel complex may form single bridges to two different metal ions in, for example, Ni 3 Cu 2 , Ni 3 Ag 2 or Ni 3 Zn 2 clusters [4,10,12,13] or Ni 4 Pd 2 paddle wheels; [10,14] they can act as a chelating ligand to one metal ion to form ion and the other one µ 3 -bridging to two copper ions. The complex is located on a crystallographic twofold axis and the complex in a single crystal is enantiomerically pure.…”