[Bis(1,3-dithiole-2-thione-4,5- dithiolato)diarylantimonate(1-)], [Ar2Sb(dmit)2]−, complexes. Crystal structures of [NEt4][Ar2Sb(dmit)2] (Ar = Ph or p-tolyl)

Howie, R. Α.; Low, John N.; Spencer, Gavin M.; Wardell, Jámes L.

doi:10.1016/s0277-5387(97)00004-1

Cited by 10 publications

(8 citation statements)

References 9 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Deep red crystals were obtained by slow diffusion of hexane into a solution of 9 in THF. 1 H NMR and IR spectra are in good agreement with already published data . The 13 C NMR spectrum was not reported in ref ; therefore, it is presented here.…”

Section: Methodssupporting

confidence: 91%

“…1 H NMR and IR spectra are in good agreement with already published data . The 13 C NMR spectrum was not reported in ref ; therefore, it is presented here.…”

Section: Methodssupporting

confidence: 91%

“…One can note the cis arrangement of the phenyl groups; therefore, each dithiolene ligand is unsymmetric, with distances slightly longer for the Sb−S bonds trans to Sb−C ipso than for the pair of Sb−S bonds trans to each other. Nevertheless, bond lengths and angles are in the usual range. , Both dithiolene ligands are highly folded along the S- - -S hinge, back toward the phenyl rings, in a face-to face conformation, with calculated values for the dihedral angles of 43.08° (S1- - -S2) and 39.64° (S5- - -S6) (Table ).…”

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Neutral and Dianionic Organoantimony(III) Dithiolene Complexes: Syntheses, X-ray Crystal Structures, and Unexpected Reactivity

Avarvari

Fourmigué

2003

Organometallics

View full text Add to dashboard Cite

The new neutral PhSb(dmid) (dmid 2-) 4,5-dithiolato-1,3-dithiol-2-one) complex has been synthesized upon reaction of deprotected 1,3,4,6-tetrathiapentalene-2,5-dione with dichlorophenylstibine. Single-crystal X-ray structure determination shows an original threedimensional network in the solid state, via Sb---O and Sb---S secondary interactions, based on an octagonal "Sb 4 S 4 " motif. Not only PhSb(dmid) but also PhSb(dmit) (dmit 2-) 4,5dithiolato-1,3-dithiole-2-thione) reacts with a second 1 equiv of dithiolate to give a series of highly reactive dianionic complexes, unknown so far. One of these complexes, [Me 4 N] 2 [PhSb-(dmid) 2 ], was structurally characterized by single-crystal X-ray measurements. Both dithiolene ligands, lying in the equatorial plane of a distorted octahedron, are unsymmetrically coordinated, with two Sb-S distances much longer than the other two. These dianionic species reacted with 1 equiv of PhSbCl 2 to give, unexpectedly, a series of Sb(V) [Ph 2 Sb(dithiolene) 2 ]complexes. The same compounds were obtained directly upon slow addition of 1 equiv of PhSbCl 2 on the corresponding dithiolate suspensions. This demonstrates that dianionic [PhSb III (dithiolene) 2 ] 2species are key intermediates in the synthesis of [Ph 2 Sb V (dithiolene) 2 ]salts. The single-crystal X-ray structure determination of the tetraethylammonium salts of [Ph 2 Sb(dmid) 2 ] -, [Ph 2 Sb(dmit) 2 ] -, and [Ph 2 Sb(dmid)(dmit)]show a distorted-octahedral coordination geometry for the Sb center with a cis configuration of the phenyl groups. This is preserved also in solution, as established by 13 C NMR. Using the same technique, combined with 1 H NMR, in a scrambling experiment, a fast dithiolene exchange has been emphasized. In the case of the [Ph 2 Sb(dmid) 2 ]salt, two polymorphs, with different folding angles along the S---S hinge, were crystallized.

show abstract

Section: Methodssupporting

confidence: 91%

“…1 H NMR and IR spectra are in good agreement with already published data . The 13 C NMR spectrum was not reported in ref ; therefore, it is presented here.…”

Section: Methodssupporting

confidence: 91%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Neutral and Dianionic Organoantimony(III) Dithiolene Complexes: Syntheses, X-ray Crystal Structures, and Unexpected Reactivity

Avarvari

Fourmigué

2003

Organometallics

View full text Add to dashboard Cite

show abstract

“…Among these complexes are inorganic and organometallic Sb V compounds, e.g., [Q][Sb(dmit) 3 ] (1) [4], [Q][Ar 2 Sb(dmit) 2 ] [5,6] (2) and Sb III species, such as [Q][Sb(dmit) 2 ] (3) [7][8][9][10] and PhSb(dmit)(THF) (4) [11] (Ar = Ph or p-tolyl; Q = onium cation). In contrast to the Sb V ionic complexes, 1-2, the Sb III ionic complex, 3, exhibits inter-anion Sb-S interactions: however, all the Sb centers in 1-3 are 6-coordinate, in the case of 3 excluding the Sb lone pair.…”

mentioning

confidence: 99%

“…3a. Bond lengths and bond angles relating to the coordination of the Sb atom are given in Table 1 [20] and in [(CO) 5 Cr]2Sb(Cl)(THF), 2.236 Å , [21]. The intra-and inter-molecular Sb-S bond lengths in 5 can be compared with the corresponding intra-and inter-molecular bonds [9] compared with the sum of the van der Waals radii of Sb and S of 4.06 Å [19].…”

mentioning

confidence: 99%