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V. V. Sharutin - One of the best experts on this subject based on the ideXlab platform.
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Synthesis and Structure of Organyltriphenylphosphonium and Stibonium Hexabromoplatinates
Russian Journal of General Chemistry, 2020Co-Authors: A. R. Zykova, V. V. Sharutin, O. K. Sharutina, V. S. SenchurinAbstract:Organyltriphenylphosphonium and -Stibonium hexabromoplatinates were synthesized by the reaction of potassium hexabromoplatinate with organyltriphenylphosphonium and -Stibonium bromides in acetonitrile or water. The complexes [Ph_3PC_2H_5]_2[PtBr_6] and [Ph_3PCH_2Ph]_2[PtBr_6] were obtained by recrystallization from dimethyl sulfoxide; the complexes [Ph_3PCH_2Ph][PtBr_5(Et_2SO-S)] and [Ph_4Sb·Et_2SO-O]_2[PtBr_6], by recrystallization of benzyltriphenylphosphonium and tetraphenylStibonium hexabromoplatinates from diethyl sulfoxide. According to the X-ray data, phosphorus atoms in cations have a distorted tetrahedral coordination and antimony atoms, a distorted trigonal-bipyramidal coordination due caused by the Sb···O=SEt_2 interaction.
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Synthesis and structures of zirconium complexes [Et_2H_2N]^+_2[ZrCl_6]^2–, [Me_3NCH_2Ph]^+_2[ZrCl_6]^2–•MeCN, [Ph_3PC_6H_4(CHPh_2-4)]^+_2[ZrCl_6]^2–•2 MeCN, and [Ph_4Sb]^+_2[ZrCl_6]^2–
Russian Chemical Bulletin, 2019Co-Authors: V. V. Sharutin, O. K. Sharutina, N. M. Tarasova, O. S. El′tsovAbstract:The complexes [Et_2H_2N]^+_2[ZrCl_6]^2– ( 1 ), [Me_3NCH_2Ph]^+_2[ZrCl_6]^2–•MeCN ( 2 ), [Ph_3PC_6H_4(CHPh_2-4)]^+_2[ZrCl_6]^2–•2 MeCN ( 3 ), and [Ph_4Sb]^+_2[ZrCl_6]^2– ( 4 ) were synthesized by the reaction of zirconium tetrachloride with tetraorganylammonium, -phosphonium, and -Stibonium chlorides in acetonitrile and structurally characterized. The nitrogen, phosphorus, and antimony atoms in the cations have a distorted tetrahedral geometry. The Zr–Cl distances in the centrosymmetric octahedral [ZrCl_6]^2− anions of complexes 1–4 have similar values, the longest bonds being observed in the anion of complex 4 . Acetonitrile molecules are involved in the structural organization of the crystals of complex 3 via weak hydrogen bonding with phenyl hydrogen atoms of the organylphosphonium cations. In the crystal of 2 , no hydrogen bonds between the cations and solvent molecules are observed; acetonitrile molecules fill the cavities formed by cations and anions.
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Bismuth complexes [p-Tol_4P] _2 ^+ [Bi_2I_8(THF)_2]^2–, [p-Tol_4Sb] _2 ^+ [Bi_2I_8(THF)_2]^2–, [p-Tol_4P] _2 ^+
Russian Journal of Inorganic Chemistry, 2017Co-Authors: V. V. Sharutin, O. K. Sharutina, R. M. Khisamov, V. S. SenchurinAbstract:The complexes [ p -Tol_4P] _2 ^+ [Bi_2I_8(THF)_2]^2–, [ p -Tol_4Sb] _2 ^+ [Bi_2I_8(THF)_2]^2–, [ p -Tol_4P] _2 ^+ [Bi_2I_8(DMSO)_2]^2–, [Bu_4P] _ n ^+ [(Bi_2I_7)_ n ]^ n –, [ p -Tol_4P]_ n ^+[(Bi_2I_7)_ n ]^ n –, and [ p -Tol_4Sb] _ n ^+ [(Bi_2I_7)_ n ]^ n – were synthesized by the reaction between bismuth iodides and tetrabutyl- and tetraphenylphosphonium, tetra- para -tolylphosphonium and -Stibonium iodides in tetrahydrofuran, dimethyl sulfoxide, acetone, and ethyl cellosolve. The crystal structures of the synthesized complexes containing bi- and polynuclear anions with an octahedral coordination of bismuth atoms were characterized by X-ray diffraction.
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Synthesis and structure of the rhodium complex [p-Tol_4Sb(DMSO-O)] _2 ^+ [trans-RhBr_4(DMSO-S)_2]^–[cis-RhBr_4(DMSO-S)_2]^–
Russian Journal of Coordination Chemistry, 2016Co-Authors: V. V. Sharutin, O. K. Sharutina, V. S. Senchurin, N. V. SomovAbstract:The complex [ p -(Tol)_4Sb(DMSO-O) _2 ^+ [ trans -RhBr4(DMSO-S)2]–[ cis -RhBr_4(DMSO-S)_2]^– (CIF file CCDC no. 1415243) was synthesized by the reaction of sodium hexabromorhodate with tetra( para -tolyl) Stibonium bromide in DMSO and studied by X-ray diffraction. The antimony atoms in two types of crystallographically independent [ p -Tol_4Sb(DMSO-O)]^+ cations have a distorted trigonal-bipyramidal coordination with axially arranged DMSO oxygen atoms (Sb–C, 2.088(9)–2.135(10) Å; Sb∙∙∙O, 2.641(10), 2.690(10) Å). In the octahedral [ trans -RhBr_4(DMSO-S)_2]^– and [ cis -RhBr_4(DMSO-S)_2]^– anions, the dimethyl sulfoxide ligands are coordinated to the metal via the sulfur atoms. The Rh–S distances are longer in the trans -isomer (2.333(2), 2.339(2) Å) than in the cis -isomer (2.303(3), 2.318(4) Å).
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Iridium complexes [p-Tol_4Sb]^+[p-Tol_4Sb(DMSO)]^+[IrBr_6]^2– and [p-Tol_4Sb(DMSO)]^+[IrBr_4(DMSO)_2]^–: Synthesis and structure
Russian Journal of Inorganic Chemistry, 2016Co-Authors: V. V. Sharutin, O. K. Sharutina, V. S. Senchurin, N. V. SomovAbstract:The complex [ p -Tol_4Sb]^+[ p -Tol_4Sb(DMSO)]^+[IrBr_6]^2– ( I ) has been synthesized by the reaction between tetra(para-tolyl)Stibonium bromide and sodium hexabromoiridate(IV) in dimethyl sulfoxide. In a solution, complex I is slowly converted into [ p -Tol_4Sb(DMSO)]^+[IrBr_4(DMSO)_2]^– ( II ). The antimony atoms in the [ p -Tol_4Sb]^+ cation of complex I have a distorted tetrahedral coordination: СSbС angles are 106.5(3)°–111.1(3)°, and Sb–С bonds range within 2.083(7)–2.097(7) Å. The antimony atoms in [ p -Tol_4Sb(DMSO)]^+ cations have a distorted trigonal bipyramidal coordination to oxygen and carbon atoms in axial positions. The axial OSbC and equatorial СSbC angles are, respectively, 172.5(4)° and 107.6(3)°, 115.9(3)°, 120.0(3)° for I ; 177.2(9)° and 113.7(9)°, 116.9(9)°, 117.8(9)° for II . The Sb–C and Sb–O distances are 2.086(7)–2.117(8) and 2.945(9) Å ( I ), 2.09(2)–2.16(2) and 2.60(2) Å ( II ). The trans -BrIrBr angles in the octahedral [IrBr_6]^2– and [IrBr_4(DMSO)_2]^– anions range within 178.79(3)°–179.49(3)° and 176.6(4)°–178.79(15)°, respectively. The Ir–Br distances are 2.4686(9)–2.4925(9) Å and 2.463(5)–2.500(4) Å, respectively, and the Ir–S distances are 2.291(7) and 2.340(5) Å.
François P. Gabbaï - One of the best experts on this subject based on the ideXlab platform.
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redox controlled chalcogen and pnictogen bonding the case of a sulfonium Stibonium dication as a preanionophore for chloride anion transport
Chemical Science, 2020Co-Authors: Gyeongjin Park, François P. GabbaïAbstract:Our interest in the chemistry of tunable chalcogen and pnictogen bond donors as Lewis acidic platforms for the complexation and transport of anions has led us to investigate examples of such compounds that can be activated by redox events. Here, we describe the synthesis of [o-MePhS(C6H4)SbPh3]2+ ([3]2+) and [o-MePhS(C6H4)Sb(p-Tol)3]2+ ([4]2+), two dicationic Stibonium/sulfonium bifunctional Lewis acids which were obtained by methylation of the phenylthioether derivatives [o-PhS(C6H4)SbPh3]+ ([1]+) and [o-PhS(C6H4)Sb(p-Tol)3]+ ([2]+), respectively. An evaluation of the chloride anion transport properties of these derivatives using chloride-loaded POPC unilamellar vesicles shows that the activity of the monocations [1]+ and [2]+ greatly exceeds that of the dications [3]2+ and [4]2+, a phenomenon that we assign to the higher lipophilicity of the monocationic compounds. Harnessing this large transport activity differential, we show that [4]2+ can be used as a prechloridophore that is readily activated by reduction of the sulfonium moiety. Indeed, [4]2+ reacts with GSH to afford [2]+ as an active transporter. This activation, which has been monitored in aqueous solution, can also be carried out in situ, in the presence of the chloride-loaded POPC unilamellar vesicles.
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Redox-controlled chalcogen and pnictogen bonding: the case of a sulfonium/Stibonium dication as a preanionophore for chloride anion transport
Chemical Science, 2020Co-Authors: Gyeongjin Park, François P. GabbaïAbstract:Our interest in the chemistry of tunable chalcogen and pnictogen bond donors as Lewis acidic platforms for the complexation and transport of anions has led us to investigate examples of such compounds that can be activated by redox events. Here, we describe the synthesis of [o-MePhS(C6H4)SbPh3]2+ ([3]2+) and [o-MePhS(C6H4)Sb(p-Tol)3]2+ ([4]2+), two dicationic Stibonium/sulfonium bifunctional Lewis acids which were obtained by methylation of the phenylthioether derivatives [o-PhS(C6H4)SbPh3]+ ([1]+) and [o-PhS(C6H4)Sb(p-Tol)3]+ ([2]+), respectively. An evaluation of the chloride anion transport properties of these derivatives using chloride-loaded POPC unilamellar vesicles shows that the activity of the monocations [1]+ and [2]+ greatly exceeds that of the dications [3]2+ and [4]2+, a phenomenon that we assign to the higher lipophilicity of the monocationic compounds. Harnessing this large transport activity differential, we show that [4]2+ can be used as a prechloridophore that is readily activated by reduction of the sulfonium moiety. Indeed, [4]2+ reacts with GSH to afford [2]+ as an active transporter. This activation, which has been monitored in aqueous solution, can also be carried out in situ, in the presence of the chloride-loaded POPC unilamellar vesicles.
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Phosphonium-Stibonium and bis-Stibonium cations as pnictogen-bonding catalysts for the transfer hydrogenation of quinolines.
Dalton transactions (Cambridge England : 2003), 2019Co-Authors: Mengxi Yang, Masato Hirai, François P. GabbaïAbstract:Bifunctional Lewis acidic group 15 compounds have emerged as appealing platforms for anion sensing and organocatalysis. As part of our interest in the chemistry of these compounds, we have now compared the catalytic properties of [o-(MePPh2)C6H4SbPh2]+ ([3]+), [o-(PPh2)C6H4SbPh3]+ ([4]+), [o-(MePPh2)C6H4SbPh3]2+ ([5]2+), and [o-C6H4(SbMePh2)2]2+ ([6]2+) using the transfer hydrogenation of 2-phenyl-quinoline and 3-bromoquinoline with a Hantzsch ester benchmark reactions. This study, which also involved an evaluation of the catalytic properties of [Ph4Sb]+ and [Ph3MeP]+, shows that antimony cations are generally more active than their phosphorus counterparts and neutral stiboranes. Our results also demonstrate that dicationic systems such as [6]2+ are superior activators.
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Influence of the catalyst structure in the cycloaddition of isocyanates to oxiranes promoted by tetraarylStibonium cations.
Dalton transactions (Cambridge England : 2003), 2018Co-Authors: Mengxi Yang, Nilanjana Pati, Guillaume Bélanger-chabot, Masato Hirai, François P. GabbaïAbstract:In the context of our work on electron deficient group 15 cations as Lewis acid catalysts, we have synthesized the triflate salts of a series of tetraarylStibonium cations of general formula [ArSbPh3]+ with Ar = Mes (4+), o-(dimethylamino)phenyl (5+), and o-((dimethylamino)methyl)phenyl (6+). These new cationic antimony derivatives, along with the known [Ph4Sb]+ (1+), 1-naphthyltriphenylStibonium (2+), and [(Ant)SbPh3]+ (3+), have been evaluated as catalysts for the cycloaddition of oxiranes and isocyanates under mild conditions. While all Stibonium cations favor the 3,4-oxazolidinone products, the reactivities of 5+ and 6+ are hindered by the ancillary amino donor which quenches the Lewis acidity of the antimony center. A comparison of the other Stibonium cations shows that 4+ is the most selective catalyst.
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OFF–ON Fluorescence Sensing of Fluoride by Donor–Antimony(V) Lewis Acids
Organometallics, 2017Co-Authors: Ajay Kumar, François P. Gabbaï, Mengxi Yang, Minji Kim, Min Hyung LeeAbstract:A series of triarylmethylStibonium Lewis acids of general formula [Ph2MeSb-(p-(C6H4))-FLUO]+ bearing a peripheral electron-rich fluorophore (FLUO = 10H-phenoxazine ([3a]+), diphenylamine ([3b]+), and 9H-carbazole ([3c]+)) have been synthesized and investigated for the fluorescence turn-on sensing of fluoride anions. Treatment of the Stibonium cations with fluoride anions leads to the corresponding fluorostiboranes (3a-F–3c-F). While the Stibonium cations are almost nonemissive, the fluorostiboranes display fluorophore-centered emissions arising from the corresponding π–π* excited state. The carbazole-containing derivative [3c]+ exhibits the most intense fluorescence turn-on response. It also displays a high binding constant (K > 107 M–1) in MeCN and shows compatibility with protic media such as MeOH (K = 950(±50) M–1). Computational studies aimed at identifying the origin of the turn-on response show that the excited state of the Stibonium cations is best described as charge transfer in nature with the π ...
V. S. Senchurin - One of the best experts on this subject based on the ideXlab platform.
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Synthesis and Structure of Organyltriphenylphosphonium and Stibonium Hexabromoplatinates
Russian Journal of General Chemistry, 2020Co-Authors: A. R. Zykova, V. V. Sharutin, O. K. Sharutina, V. S. SenchurinAbstract:Organyltriphenylphosphonium and -Stibonium hexabromoplatinates were synthesized by the reaction of potassium hexabromoplatinate with organyltriphenylphosphonium and -Stibonium bromides in acetonitrile or water. The complexes [Ph_3PC_2H_5]_2[PtBr_6] and [Ph_3PCH_2Ph]_2[PtBr_6] were obtained by recrystallization from dimethyl sulfoxide; the complexes [Ph_3PCH_2Ph][PtBr_5(Et_2SO-S)] and [Ph_4Sb·Et_2SO-O]_2[PtBr_6], by recrystallization of benzyltriphenylphosphonium and tetraphenylStibonium hexabromoplatinates from diethyl sulfoxide. According to the X-ray data, phosphorus atoms in cations have a distorted tetrahedral coordination and antimony atoms, a distorted trigonal-bipyramidal coordination due caused by the Sb···O=SEt_2 interaction.
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Bismuth complexes [p-Tol_4P] _2 ^+ [Bi_2I_8(THF)_2]^2–, [p-Tol_4Sb] _2 ^+ [Bi_2I_8(THF)_2]^2–, [p-Tol_4P] _2 ^+
Russian Journal of Inorganic Chemistry, 2017Co-Authors: V. V. Sharutin, O. K. Sharutina, R. M. Khisamov, V. S. SenchurinAbstract:The complexes [ p -Tol_4P] _2 ^+ [Bi_2I_8(THF)_2]^2–, [ p -Tol_4Sb] _2 ^+ [Bi_2I_8(THF)_2]^2–, [ p -Tol_4P] _2 ^+ [Bi_2I_8(DMSO)_2]^2–, [Bu_4P] _ n ^+ [(Bi_2I_7)_ n ]^ n –, [ p -Tol_4P]_ n ^+[(Bi_2I_7)_ n ]^ n –, and [ p -Tol_4Sb] _ n ^+ [(Bi_2I_7)_ n ]^ n – were synthesized by the reaction between bismuth iodides and tetrabutyl- and tetraphenylphosphonium, tetra- para -tolylphosphonium and -Stibonium iodides in tetrahydrofuran, dimethyl sulfoxide, acetone, and ethyl cellosolve. The crystal structures of the synthesized complexes containing bi- and polynuclear anions with an octahedral coordination of bismuth atoms were characterized by X-ray diffraction.
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Synthesis and structure of the rhodium complex [p-Tol4Sb(DMSO-O)]2+[trans-RhBr4(DMSO-S)2]–[cis-RhBr4(DMSO-S)2]–
Russian Journal of Coordination Chemistry, 2016Co-Authors: Vladimir V. Sharutin, V. S. Senchurin, Olga K. Sharutina, N. V. SomovAbstract:The complex [p-(Tol)4Sb(DMSO-O)2+[trans-RhBr4(DMSO-S)2]–[cis-RhBr4(DMSO-S)2]– (CIF file CCDC no. 1415243) was synthesized by the reaction of sodium hexabromorhodate with tetra(para-tolyl) Stibonium bromide in DMSO and studied by X-ray diffraction. The antimony atoms in two types of crystallographically independent [p-Tol4Sb(DMSO-O)]+ cations have a distorted trigonal-bipyramidal coordination with axially arranged DMSO oxygen atoms (Sb–C, 2.088(9)–2.135(10) A; Sb∙∙∙O, 2.641(10), 2.690(10) A). In the octahedral [trans-RhBr4(DMSO-S)2]– and [cis-RhBr4(DMSO-S)2]– anions, the dimethyl sulfoxide ligands are coordinated to the metal via the sulfur atoms. The Rh–S distances are longer in the trans-isomer (2.333(2), 2.339(2) A) than in the cis-isomer (2.303(3), 2.318(4) A).
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Synthesis and structure of the rhodium complex [p-Tol_4Sb(DMSO-O)] _2 ^+ [trans-RhBr_4(DMSO-S)_2]^–[cis-RhBr_4(DMSO-S)_2]^–
Russian Journal of Coordination Chemistry, 2016Co-Authors: V. V. Sharutin, O. K. Sharutina, V. S. Senchurin, N. V. SomovAbstract:The complex [ p -(Tol)_4Sb(DMSO-O) _2 ^+ [ trans -RhBr4(DMSO-S)2]–[ cis -RhBr_4(DMSO-S)_2]^– (CIF file CCDC no. 1415243) was synthesized by the reaction of sodium hexabromorhodate with tetra( para -tolyl) Stibonium bromide in DMSO and studied by X-ray diffraction. The antimony atoms in two types of crystallographically independent [ p -Tol_4Sb(DMSO-O)]^+ cations have a distorted trigonal-bipyramidal coordination with axially arranged DMSO oxygen atoms (Sb–C, 2.088(9)–2.135(10) Å; Sb∙∙∙O, 2.641(10), 2.690(10) Å). In the octahedral [ trans -RhBr_4(DMSO-S)_2]^– and [ cis -RhBr_4(DMSO-S)_2]^– anions, the dimethyl sulfoxide ligands are coordinated to the metal via the sulfur atoms. The Rh–S distances are longer in the trans -isomer (2.333(2), 2.339(2) Å) than in the cis -isomer (2.303(3), 2.318(4) Å).
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Iridium complexes [p-Tol_4Sb]^+[p-Tol_4Sb(DMSO)]^+[IrBr_6]^2– and [p-Tol_4Sb(DMSO)]^+[IrBr_4(DMSO)_2]^–: Synthesis and structure
Russian Journal of Inorganic Chemistry, 2016Co-Authors: V. V. Sharutin, O. K. Sharutina, V. S. Senchurin, N. V. SomovAbstract:The complex [ p -Tol_4Sb]^+[ p -Tol_4Sb(DMSO)]^+[IrBr_6]^2– ( I ) has been synthesized by the reaction between tetra(para-tolyl)Stibonium bromide and sodium hexabromoiridate(IV) in dimethyl sulfoxide. In a solution, complex I is slowly converted into [ p -Tol_4Sb(DMSO)]^+[IrBr_4(DMSO)_2]^– ( II ). The antimony atoms in the [ p -Tol_4Sb]^+ cation of complex I have a distorted tetrahedral coordination: СSbС angles are 106.5(3)°–111.1(3)°, and Sb–С bonds range within 2.083(7)–2.097(7) Å. The antimony atoms in [ p -Tol_4Sb(DMSO)]^+ cations have a distorted trigonal bipyramidal coordination to oxygen and carbon atoms in axial positions. The axial OSbC and equatorial СSbC angles are, respectively, 172.5(4)° and 107.6(3)°, 115.9(3)°, 120.0(3)° for I ; 177.2(9)° and 113.7(9)°, 116.9(9)°, 117.8(9)° for II . The Sb–C and Sb–O distances are 2.086(7)–2.117(8) and 2.945(9) Å ( I ), 2.09(2)–2.16(2) and 2.60(2) Å ( II ). The trans -BrIrBr angles in the octahedral [IrBr_6]^2– and [IrBr_4(DMSO)_2]^– anions range within 178.79(3)°–179.49(3)° and 176.6(4)°–178.79(15)°, respectively. The Ir–Br distances are 2.4686(9)–2.4925(9) Å and 2.463(5)–2.500(4) Å, respectively, and the Ir–S distances are 2.291(7) and 2.340(5) Å.
O. K. Sharutina - One of the best experts on this subject based on the ideXlab platform.
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Synthesis and Structure of Organyltriphenylphosphonium and Stibonium Hexabromoplatinates
Russian Journal of General Chemistry, 2020Co-Authors: A. R. Zykova, V. V. Sharutin, O. K. Sharutina, V. S. SenchurinAbstract:Organyltriphenylphosphonium and -Stibonium hexabromoplatinates were synthesized by the reaction of potassium hexabromoplatinate with organyltriphenylphosphonium and -Stibonium bromides in acetonitrile or water. The complexes [Ph_3PC_2H_5]_2[PtBr_6] and [Ph_3PCH_2Ph]_2[PtBr_6] were obtained by recrystallization from dimethyl sulfoxide; the complexes [Ph_3PCH_2Ph][PtBr_5(Et_2SO-S)] and [Ph_4Sb·Et_2SO-O]_2[PtBr_6], by recrystallization of benzyltriphenylphosphonium and tetraphenylStibonium hexabromoplatinates from diethyl sulfoxide. According to the X-ray data, phosphorus atoms in cations have a distorted tetrahedral coordination and antimony atoms, a distorted trigonal-bipyramidal coordination due caused by the Sb···O=SEt_2 interaction.
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Synthesis and structures of zirconium complexes [Et_2H_2N]^+_2[ZrCl_6]^2–, [Me_3NCH_2Ph]^+_2[ZrCl_6]^2–•MeCN, [Ph_3PC_6H_4(CHPh_2-4)]^+_2[ZrCl_6]^2–•2 MeCN, and [Ph_4Sb]^+_2[ZrCl_6]^2–
Russian Chemical Bulletin, 2019Co-Authors: V. V. Sharutin, O. K. Sharutina, N. M. Tarasova, O. S. El′tsovAbstract:The complexes [Et_2H_2N]^+_2[ZrCl_6]^2– ( 1 ), [Me_3NCH_2Ph]^+_2[ZrCl_6]^2–•MeCN ( 2 ), [Ph_3PC_6H_4(CHPh_2-4)]^+_2[ZrCl_6]^2–•2 MeCN ( 3 ), and [Ph_4Sb]^+_2[ZrCl_6]^2– ( 4 ) were synthesized by the reaction of zirconium tetrachloride with tetraorganylammonium, -phosphonium, and -Stibonium chlorides in acetonitrile and structurally characterized. The nitrogen, phosphorus, and antimony atoms in the cations have a distorted tetrahedral geometry. The Zr–Cl distances in the centrosymmetric octahedral [ZrCl_6]^2− anions of complexes 1–4 have similar values, the longest bonds being observed in the anion of complex 4 . Acetonitrile molecules are involved in the structural organization of the crystals of complex 3 via weak hydrogen bonding with phenyl hydrogen atoms of the organylphosphonium cations. In the crystal of 2 , no hydrogen bonds between the cations and solvent molecules are observed; acetonitrile molecules fill the cavities formed by cations and anions.
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Bismuth complexes [p-Tol_4P] _2 ^+ [Bi_2I_8(THF)_2]^2–, [p-Tol_4Sb] _2 ^+ [Bi_2I_8(THF)_2]^2–, [p-Tol_4P] _2 ^+
Russian Journal of Inorganic Chemistry, 2017Co-Authors: V. V. Sharutin, O. K. Sharutina, R. M. Khisamov, V. S. SenchurinAbstract:The complexes [ p -Tol_4P] _2 ^+ [Bi_2I_8(THF)_2]^2–, [ p -Tol_4Sb] _2 ^+ [Bi_2I_8(THF)_2]^2–, [ p -Tol_4P] _2 ^+ [Bi_2I_8(DMSO)_2]^2–, [Bu_4P] _ n ^+ [(Bi_2I_7)_ n ]^ n –, [ p -Tol_4P]_ n ^+[(Bi_2I_7)_ n ]^ n –, and [ p -Tol_4Sb] _ n ^+ [(Bi_2I_7)_ n ]^ n – were synthesized by the reaction between bismuth iodides and tetrabutyl- and tetraphenylphosphonium, tetra- para -tolylphosphonium and -Stibonium iodides in tetrahydrofuran, dimethyl sulfoxide, acetone, and ethyl cellosolve. The crystal structures of the synthesized complexes containing bi- and polynuclear anions with an octahedral coordination of bismuth atoms were characterized by X-ray diffraction.
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Synthesis and structure of the rhodium complex [p-Tol_4Sb(DMSO-O)] _2 ^+ [trans-RhBr_4(DMSO-S)_2]^–[cis-RhBr_4(DMSO-S)_2]^–
Russian Journal of Coordination Chemistry, 2016Co-Authors: V. V. Sharutin, O. K. Sharutina, V. S. Senchurin, N. V. SomovAbstract:The complex [ p -(Tol)_4Sb(DMSO-O) _2 ^+ [ trans -RhBr4(DMSO-S)2]–[ cis -RhBr_4(DMSO-S)_2]^– (CIF file CCDC no. 1415243) was synthesized by the reaction of sodium hexabromorhodate with tetra( para -tolyl) Stibonium bromide in DMSO and studied by X-ray diffraction. The antimony atoms in two types of crystallographically independent [ p -Tol_4Sb(DMSO-O)]^+ cations have a distorted trigonal-bipyramidal coordination with axially arranged DMSO oxygen atoms (Sb–C, 2.088(9)–2.135(10) Å; Sb∙∙∙O, 2.641(10), 2.690(10) Å). In the octahedral [ trans -RhBr_4(DMSO-S)_2]^– and [ cis -RhBr_4(DMSO-S)_2]^– anions, the dimethyl sulfoxide ligands are coordinated to the metal via the sulfur atoms. The Rh–S distances are longer in the trans -isomer (2.333(2), 2.339(2) Å) than in the cis -isomer (2.303(3), 2.318(4) Å).
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Iridium complexes [p-Tol_4Sb]^+[p-Tol_4Sb(DMSO)]^+[IrBr_6]^2– and [p-Tol_4Sb(DMSO)]^+[IrBr_4(DMSO)_2]^–: Synthesis and structure
Russian Journal of Inorganic Chemistry, 2016Co-Authors: V. V. Sharutin, O. K. Sharutina, V. S. Senchurin, N. V. SomovAbstract:The complex [ p -Tol_4Sb]^+[ p -Tol_4Sb(DMSO)]^+[IrBr_6]^2– ( I ) has been synthesized by the reaction between tetra(para-tolyl)Stibonium bromide and sodium hexabromoiridate(IV) in dimethyl sulfoxide. In a solution, complex I is slowly converted into [ p -Tol_4Sb(DMSO)]^+[IrBr_4(DMSO)_2]^– ( II ). The antimony atoms in the [ p -Tol_4Sb]^+ cation of complex I have a distorted tetrahedral coordination: СSbС angles are 106.5(3)°–111.1(3)°, and Sb–С bonds range within 2.083(7)–2.097(7) Å. The antimony atoms in [ p -Tol_4Sb(DMSO)]^+ cations have a distorted trigonal bipyramidal coordination to oxygen and carbon atoms in axial positions. The axial OSbC and equatorial СSbC angles are, respectively, 172.5(4)° and 107.6(3)°, 115.9(3)°, 120.0(3)° for I ; 177.2(9)° and 113.7(9)°, 116.9(9)°, 117.8(9)° for II . The Sb–C and Sb–O distances are 2.086(7)–2.117(8) and 2.945(9) Å ( I ), 2.09(2)–2.16(2) and 2.60(2) Å ( II ). The trans -BrIrBr angles in the octahedral [IrBr_6]^2– and [IrBr_4(DMSO)_2]^– anions range within 178.79(3)°–179.49(3)° and 176.6(4)°–178.79(15)°, respectively. The Ir–Br distances are 2.4686(9)–2.4925(9) Å and 2.463(5)–2.500(4) Å, respectively, and the Ir–S distances are 2.291(7) and 2.340(5) Å.
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Synthesis and structure of bismuth-containing complexes [(Ph_4BiO)_2{2,5-(CH_3)_2C_6H_3S(O)}] _2 ^+ [Ph_2Bi_2I_6]^2−,[(Ph_4Bi]^+[PhBi(C_5H_5N)I_3]^−, [Ph_4Sb] _4 ^+
Russian Journal of Coordination Chemistry, 2004Co-Authors: V. V. Sharutin, I. V. Egorova, O. K. Sharutina, O. A. Dorofeeva, T. K. Ivanenko, A. V. Gerasimenko, M. A. PushilinAbstract:The reactions of tetraphenylbismuthonium and -Stibonium salts Ph_4EX (E = Bi, Sb; X = I, OSO_2(C_6H_3(CH_3)_2−2,5), OSO_2C_6H_3(OH-4)(COOH-3)) with bismuth triiodide in acetone afford complexes [Ph_4Bi]^+[PhBi(C_5H_5N)I_3]^−, [(Ph_4BiO)_2S(O){2,5-(CH_3)_2C_6H_3S(O)}] _2 ^+ [Ph_2Bi_2I_6]^2−, [Ph_4Sb] _4 ^+ [Bi_4I_16]^4−⋅2(CH_3)_2C=O, and [Ph_4Sb] _3 ^+ [Bi_5I_18]^3−, whose structural units, according to the X-ray diffraction data, are tetraphenylbismuthonium (-Stibonium) cations and mono-, di-, tetra-, and pentanuclear anions, respectively.
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Synthesis and structure of bismuth-containing complexes [(Ph_4BiO)_2{2,5-(CH_3)_2C_6H_3S(O)} _2 ^+ [Ph_2Bi_2I_6]^2,[(Ph_4Bi]^+[PhBi(C_5H_5N)I_3]^–, [Ph_4Sb[Bi_4I_16]^4·2(CH_3)_2 C=O, and [Ph_4Sb
Russian Journal of Coordination Chemistry, 2004Co-Authors: V. V. Sharutin, I. V. Egorova, O. K. Sharutina, O. A. Dorofeeva, T. K. Ivanenko, A. V. Gerasimenko, M. A. PushilinAbstract:The reactions of tetraphenylbismuthonium and -Stibonium salts Ph_4EX (E = Bi, Sb; X = I, OSO_2 (C_6H_3(CH_3)_2-2,5), OSO_2C_6H_3(OH-4)(COOH-3)) with bismuth triiodide in acetone afford complexes [Ph_4Bi]^+[PhBi(C_5H_5N)I_3]^-, [(Ph_4BiO)_2S(O){2,5-(CH_3)_2C_6H_3S(O)} [Ph_2Bi_2I_6]^2–, [Ph_4Sb [Bi_4I_16]^4-·2(CH_3)^2C=O, and [Ph_4Sb] _3+ ^+ [Bi_5I_18]^3-, whose structural units, according to the X-ray diffraction data, are tetraphenylbismuthonium (-Stibonium) cations and mono-, di-, tetra-, and pentanuclear anions, respectively.