Preparation of [tris(1,3-dithiole-2-thione-4,5-dithiolato)antimonate(1−)] complexes, [Sbv(dmit)3]−. Crystal structure of the 1,4-dimethylpyridinium salt

Synthesis, Structural Characterization, and Biological Studies of New Antimony(III) Complexes with Thiones. The Influence of the Solvent on the Geometry of the Complexes

“…Crystal structures of antimony(III) compounds are rare in the literature due to the hydrolysis they undergo in aqueous solutions. Antimony(III)−thione complexes are found to adopt the following geometries: (i) (ψ-TBP) geometry (Scheme ) as in SbCl 3 (tmtu) (tmtu = tetramethylthiourea),8a SbCl 3 (dmit) (dmit = 1,3-dimethyl-2-( 3H )-imidazole-thione),8b 1-halo-stibathiolane of 1,2-dimethyl-propanothiolane-3,8c 1,2-diphenyl-propanothiolane-3,8c or n- hehanothiolane-6,8c {[Sb(1,2-S 2 C 6 H 4 ) 2 ] - } (1,2-S 2 C 6 H 4 = benzene-1,2-dithiol), {[Sb(dmit) 2 ] - } (H 2 -dmit = 4,5-dimercapto-1,3-dithiole-2-thione),8d and {[SbCl 2 (tHPMT) 2 ] + Cl - },8e better described, however, as a complex with a SP geometry (see crystal structure); (ii) TP geometry (Scheme ) as in Sb(SR) 3 (R−SH = 4-Me-C 6 H 4 −SH and 3,5-Me 2 -C 6 H 3 −SH) 9a and Sb(SR) 3 (R−SH = HS−C 6 H 2 - i Pr 3 -2,4,6);9b (iii) SP geometry (Scheme ) as in [SbCl 3 (NMBZT) 2 ] (NMBZT = N -methyl-2-mercapto-benzothiazole),10a [SbCl 3 (NMIM) 2 ] (NMIM = N -methyl-2-mercapto-imidazole), 10a,b [SbCl 3 (L) 2 ] (L = 1,1‘-methylene-bis(3-methyl-2H-imidazole-2-thione,10c [SbCl 3 (C 2 H 5 NHC(S)CH 2 C(S)NHC 2 H 5 )],10d [PhSb(dmit)] (H 2 -dmit = 4,5-dimercapto-1,3-dithiole-2-thione), [PhSb(pyt) 2 ] (pytH = pyridine-2-thione),10e and [mesitylSb(pyt) 2 ];10f (iv) Oh geometry (Scheme ) as in [Sb(2-SC 5 H 4 N) 3 ] and [Sb(2-SC 5 H 3 N-3-SiMe 3 ) 3 ] 11a and {[Sb(dmit) 2 ] - } (H 2 dmit = 4,5-dimercapto-1,3-dithiole-2-thione); 11b-d and (v) PP geometry (Scheme ) as in the case of [Sb(pmt) 3 ]·0.5(CH 3 OH), (pmt = 2-mercapto-pyrimidine) 12a and [Sb(2-SC 5 H 4 N) 3 ] (2-SC 5 H 4 N = 2-mercapto-pyridine) 12b…”

Synthesis, Structural Characterization, and Biological Studies of New Antimony(III) Complexes with Thiones. The Influence of the Solvent on the Geometry of the Complexes

“…Crystal structures of antimony(III) compounds are rare in the literature due to the hydrolysis they undergo in aqueous solutions. Antimony(III)−thione complexes are found to adopt the following geometries: (i) (ψ-TBP) geometry (Scheme ) as in SbCl 3 (tmtu) (tmtu = tetramethylthiourea),8a SbCl 3 (dmit) (dmit = 1,3-dimethyl-2-( 3H )-imidazole-thione),8b 1-halo-stibathiolane of 1,2-dimethyl-propanothiolane-3,8c 1,2-diphenyl-propanothiolane-3,8c or n- hehanothiolane-6,8c {[Sb(1,2-S 2 C 6 H 4 ) 2 ] - } (1,2-S 2 C 6 H 4 = benzene-1,2-dithiol), {[Sb(dmit) 2 ] - } (H 2 -dmit = 4,5-dimercapto-1,3-dithiole-2-thione),8d and {[SbCl 2 (tHPMT) 2 ] + Cl - },8e better described, however, as a complex with a SP geometry (see crystal structure); (ii) TP geometry (Scheme ) as in Sb(SR) 3 (R−SH = 4-Me-C 6 H 4 −SH and 3,5-Me 2 -C 6 H 3 −SH) 9a and Sb(SR) 3 (R−SH = HS−C 6 H 2 - i Pr 3 -2,4,6);9b (iii) SP geometry (Scheme ) as in [SbCl 3 (NMBZT) 2 ] (NMBZT = N -methyl-2-mercapto-benzothiazole),10a [SbCl 3 (NMIM) 2 ] (NMIM = N -methyl-2-mercapto-imidazole), 10a,b [SbCl 3 (L) 2 ] (L = 1,1‘-methylene-bis(3-methyl-2H-imidazole-2-thione,10c [SbCl 3 (C 2 H 5 NHC(S)CH 2 C(S)NHC 2 H 5 )],10d [PhSb(dmit)] (H 2 -dmit = 4,5-dimercapto-1,3-dithiole-2-thione), [PhSb(pyt) 2 ] (pytH = pyridine-2-thione),10e and [mesitylSb(pyt) 2 ];10f (iv) Oh geometry (Scheme ) as in [Sb(2-SC 5 H 4 N) 3 ] and [Sb(2-SC 5 H 3 N-3-SiMe 3 ) 3 ] 11a and {[Sb(dmit) 2 ] - } (H 2 dmit = 4,5-dimercapto-1,3-dithiole-2-thione); 11b-d and (v) PP geometry (Scheme ) as in the case of [Sb(pmt) 3 ]·0.5(CH 3 OH), (pmt = 2-mercapto-pyrimidine) 12a and [Sb(2-SC 5 H 4 N) 3 ] (2-SC 5 H 4 N = 2-mercapto-pyridine) 12b…”

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

“…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 ).…”

Vibrational and Electronic Spectroscopy of Neutral Antimony Coordination Compounds of the 1,3-Dithiole-2-thione-4,5-dithiolate (dmit)

“…The vibrational experimental spectra were evaluated individually. Although intermolecular interactions Sb---S and weaker S---S contacts in [SbBr­(dmit)­THF] and [NEt 4 ]­[Sb­(dmit) 2 ] have been confirmed by X-ray crystallography, these interactions were neglected in the present work, so the complexes were considered solely as isolated units. − ,− The same approach was employed in a previous theoretical work on vibrational and UV–vis spectroscopy of a series of anionic dmit and dmio (1,3-dithiole-2-one-4,5-dithiolate) complexes, and good agreement between calculated and experimental data , was obtained.…”

Synthesis, Structural Characterization, and Biological Studies of New Antimony(III) Complexes with Thiones. The Influence of the Solvent on the Geometry of the Complexes

“…Crystal structures of antimony(III) compounds are rare in the literature due to the hydrolysis they undergo in aqueous solutions. Antimony(III)−thione complexes are found to adopt the following geometries: (i) (ψ-TBP) geometry (Scheme ) as in SbCl 3 (tmtu) (tmtu = tetramethylthiourea),8a SbCl 3 (dmit) (dmit = 1,3-dimethyl-2-( 3H )-imidazole-thione),8b 1-halo-stibathiolane of 1,2-dimethyl-propanothiolane-3,8c 1,2-diphenyl-propanothiolane-3,8c or n- hehanothiolane-6,8c {[Sb(1,2-S 2 C 6 H 4 ) 2 ] - } (1,2-S 2 C 6 H 4 = benzene-1,2-dithiol), {[Sb(dmit) 2 ] - } (H 2 -dmit = 4,5-dimercapto-1,3-dithiole-2-thione),8d and {[SbCl 2 (tHPMT) 2 ] + Cl - },8e better described, however, as a complex with a SP geometry (see crystal structure); (ii) TP geometry (Scheme ) as in Sb(SR) 3 (R−SH = 4-Me-C 6 H 4 −SH and 3,5-Me 2 -C 6 H 3 −SH) 9a and Sb(SR) 3 (R−SH = HS−C 6 H 2 - i Pr 3 -2,4,6);9b (iii) SP geometry (Scheme ) as in [SbCl 3 (NMBZT) 2 ] (NMBZT = N -methyl-2-mercapto-benzothiazole),10a [SbCl 3 (NMIM) 2 ] (NMIM = N -methyl-2-mercapto-imidazole), 10a,b [SbCl 3 (L) 2 ] (L = 1,1‘-methylene-bis(3-methyl-2H-imidazole-2-thione,10c [SbCl 3 (C 2 H 5 NHC(S)CH 2 C(S)NHC 2 H 5 )],10d [PhSb(dmit)] (H 2 -dmit = 4,5-dimercapto-1,3-dithiole-2-thione), [PhSb(pyt) 2 ] (pytH = pyridine-2-thione),10e and [mesitylSb(pyt) 2 ];10f (iv) Oh geometry (Scheme ) as in [Sb(2-SC 5 H 4 N) 3 ] and [Sb(2-SC 5 H 3 N-3-SiMe 3 ) 3 ] 11a and {[Sb(dmit) 2 ] - } (H 2 dmit = 4,5-dimercapto-1,3-dithiole-2-thione); 11b-d and (v) PP geometry (Scheme ) as in the case of [Sb(pmt) 3 ]·0.5(CH 3 OH), (pmt = 2-mercapto-pyrimidine) 12a and [Sb(2-SC 5 H 4 N) 3 ] (2-SC 5 H 4 N = 2-mercapto-pyridine) 12b…”

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

“…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 ).…”

Vibrational and Electronic Spectroscopy of Neutral Antimony Coordination Compounds of the 1,3-Dithiole-2-thione-4,5-dithiolate (dmit)

“…The vibrational experimental spectra were evaluated individually. Although intermolecular interactions Sb---S and weaker S---S contacts in [SbBr­(dmit)­THF] and [NEt 4 ]­[Sb­(dmit) 2 ] have been confirmed by X-ray crystallography, these interactions were neglected in the present work, so the complexes were considered solely as isolated units. − ,− The same approach was employed in a previous theoretical work on vibrational and UV–vis spectroscopy of a series of anionic dmit and dmio (1,3-dithiole-2-one-4,5-dithiolate) complexes, and good agreement between calculated and experimental data , was obtained.…”

Synthesis, Structural Characterization, and Biological Studies of New Antimony(III) Complexes with Thiones. The Influence of the Solvent on the Geometry of the Complexes

“…Crystal structures of antimony(III) compounds are rare in the literature due to the hydrolysis they undergo in aqueous solutions. Antimony(III)−thione complexes are found to adopt the following geometries: (i) (ψ-TBP) geometry (Scheme ) as in SbCl 3 (tmtu) (tmtu = tetramethylthiourea),8a SbCl 3 (dmit) (dmit = 1,3-dimethyl-2-( 3H )-imidazole-thione),8b 1-halo-stibathiolane of 1,2-dimethyl-propanothiolane-3,8c 1,2-diphenyl-propanothiolane-3,8c or n- hehanothiolane-6,8c {[Sb(1,2-S 2 C 6 H 4 ) 2 ] - } (1,2-S 2 C 6 H 4 = benzene-1,2-dithiol), {[Sb(dmit) 2 ] - } (H 2 -dmit = 4,5-dimercapto-1,3-dithiole-2-thione),8d and {[SbCl 2 (tHPMT) 2 ] + Cl - },8e better described, however, as a complex with a SP geometry (see crystal structure); (ii) TP geometry (Scheme ) as in Sb(SR) 3 (R−SH = 4-Me-C 6 H 4 −SH and 3,5-Me 2 -C 6 H 3 −SH) 9a and Sb(SR) 3 (R−SH = HS−C 6 H 2 - i Pr 3 -2,4,6);9b (iii) SP geometry (Scheme ) as in [SbCl 3 (NMBZT) 2 ] (NMBZT = N -methyl-2-mercapto-benzothiazole),10a [SbCl 3 (NMIM) 2 ] (NMIM = N -methyl-2-mercapto-imidazole), 10a,b [SbCl 3 (L) 2 ] (L = 1,1‘-methylene-bis(3-methyl-2H-imidazole-2-thione,10c [SbCl 3 (C 2 H 5 NHC(S)CH 2 C(S)NHC 2 H 5 )],10d [PhSb(dmit)] (H 2 -dmit = 4,5-dimercapto-1,3-dithiole-2-thione), [PhSb(pyt) 2 ] (pytH = pyridine-2-thione),10e and [mesitylSb(pyt) 2 ];10f (iv) Oh geometry (Scheme ) as in [Sb(2-SC 5 H 4 N) 3 ] and [Sb(2-SC 5 H 3 N-3-SiMe 3 ) 3 ] 11a and {[Sb(dmit) 2 ] - } (H 2 dmit = 4,5-dimercapto-1,3-dithiole-2-thione); 11b-d and (v) PP geometry (Scheme ) as in the case of [Sb(pmt) 3 ]·0.5(CH 3 OH), (pmt = 2-mercapto-pyrimidine) 12a and [Sb(2-SC 5 H 4 N) 3 ] (2-SC 5 H 4 N = 2-mercapto-pyridine) 12b…”

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

“…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 ).…”

Vibrational and Electronic Spectroscopy of Neutral Antimony Coordination Compounds of the 1,3-Dithiole-2-thione-4,5-dithiolate (dmit)

“…The vibrational experimental spectra were evaluated individually. Although intermolecular interactions Sb---S and weaker S---S contacts in [SbBr­(dmit)­THF] and [NEt 4 ]­[Sb­(dmit) 2 ] have been confirmed by X-ray crystallography, these interactions were neglected in the present work, so the complexes were considered solely as isolated units. − ,− The same approach was employed in a previous theoretical work on vibrational and UV–vis spectroscopy of a series of anionic dmit and dmio (1,3-dithiole-2-one-4,5-dithiolate) complexes, and good agreement between calculated and experimental data , was obtained.…”