Interplay of Structural Flexibility and Crystal Packing in a Series of Paramagnetic Cyclopentadienyl/Dithiolene Mo and W Complexes: Evidence for Molecular Spin Ladders

Abstract

2À (2-oxo-1,3-dithiole-4,5-dithiolate), and dsit 2À (2-thioxo-1,3-dithiole-4,5-diselenolate) as dithiolene ligand are oxidized to the six corresponding 1:1 charge-transfer salts with TCNQF 4

[Cp*W(dmit)2]•: An Organometallic 15-Electron Neutral Radical (d1) with Optical Limiting Properties in Solution and an Antiferromagnetic Ground State in the Solid State

“…[20] Important bond distances and angles are reported in Table 1. Comparison with the Mo analog shows a weak shortening of the metal±sulfur bond, an effect known to be due to the relativistic effects of the heavier elements, [27] observed to a larger extent in the [Cp 2 M(dithiolene)] 0,1+ series [28] or the [M(dithiolene) 3 ] 2±,1±,0 series [29] (M = Mo, W), for example. Also, of particular note is the symmetrical folding of the two MS 2 C 2 metallacycles along the S±S hinge, close to 18 and comparable to that observed in [PPh 4 ][Cp*Mo(dmit) 2 ].…”

Crystal structures of [Rh(η5-C5H5)(C3S5)] and [Rh(η5-C5Me5)(C3S5)]2 and properties of their oxidized species

“…Cyclopentadienyl-and pentamethylcyclopentadienyl-metal complexes with the C 3 S 5 -ligand are of much interest on their oxidation. Although several metal complexes of these types have been studied and their structures clarified [4][5][6][7][8][9][10][11][12][13][14][15][16][17], there are few reports on their oxidation [14,16,17]. Upon oxidation of these complexes, the C 3 S 5 ligand-centered oxidation is expected to occur, as observed for other oxidized C 3 S 5 -metal complexes [17][18][19][20].…”

Synthesis of μ-C2S44− Cobalt Complexes by Activation of the 1,3,4,6-tetrathiapentalene-2,5-dione, and Electrochemical Study of [(Cp*Co)2(μ-C2S4)]

“…The stoichiometry of 5 was ascertained from the elemental analysis. Despite the tendency of the TCNQF 4 Ϫ· to form dimeric dianionic moieties, [20] the elemental analysis suggests that the dication [(Cp*Co) 2 (µ-C 2 S 4 )] 2ϩ is stabilized by the coordination of the anionic TCNQF 4 Ϫ· on both cobalt atoms. Unfortunately, all our attempts to grow crystals of 4 and 5 were unsuccessful.…”