Synthese und Eigenschaften von Ph₃Sn‐substituierten Telluraten – Die Kristallstrukturen von trans‐[(Ph₃SnO)₄Te(OH)₂] und trans‐[(Ph₃SnO)₂Te(OMe)₄]

Abstract

The reaction of Te(OH)6 with Ph3SnOH in ethanol leads to the formation of trans‐[(Ph3SnO)4Te(OH)2] (1). Compound 1 crystallizes triclinic in the space group P\bar{1} with a = 996.6(2) pm, b = 1365.4(3) pm, c = 1368.2(3) pm and α = 71.15(2)°, β = 71.48(2)°, γ = 74.81(3)° (at 220 K). The molecular structure of 1 consists of a tellurium atom, which is coordinated nearly octahedrally by four Ph3SnO units and two hydroxyl groups that are trans to each other. The Te–O bond lengths are in the range of 190.5(2) and 193.7(2) pm. Treatment of 1 with methanol under reflux yields trans‐[(Ph3SnO)2Te(OMe)4] (2). Compound 2 crystallizes triclinic in the space group P\bar{1} with a = 1012.8(1) pm, b = 1422.4(2) pm, c = 1618.1(2) pm, and α = 100.44(1)°, β = 107.92(1)°, γ = 110.66(1)° (at 220 K). 2 forms centrosymmetric molecules in which the tellurium atom is surrounded nearly octahedrally by four methoxy groups and two trans arranged Ph3SnO units. The Te–O bond lengths of 187.9(3)–194.5(3) pm are similar to those observed in 1.

Two-Electron Redox Chemistry at the Dinuclear Core of a TePt Platform: Chlorine Photoreductive Elimination and Isolation of a TeVPtI Complex

“…The presence of a Te–Pt bond is unambiguously confirmed by a Te-Pt bond distance of 2.5238(5) Å which is almost identical to that in [ 1 ] + (2.5281(5) Å). The short Te–F (1.954(2) Å), Te–O(1) (1.993(3) Å), and Te–O(2) (1.988(2) (2) Å) bonds are comparable to those observed for other hexavalent tellurium species with similar linkages (Te–F = 2.011 (2) Å in Ph 5 TeF, Te–O = 1.930(3) and 1.945(4) Å in (Ph 3 SnO) 2 Te­(OMe) 4 ) . To our knowledge, compound 4 is the first example of a hexavalent tellurium ligand in the coordination sphere of a metal.…”

“…The (2) Å) bonds are comparable to those observed for other hexavalent tellurium species with similar linkages (Te−F = 2.011 (2) Å in Ph 5 TeF, 24 Te−O = 1.930(3) and 1.945(4) Å in (Ph 3 SnO) 2 Te(OMe) 4 ). 27 To our knowledge, compound 4 is the first example of a hexavalent tellurium ligand in the coordination sphere of a metal. Indeed, while telluroether complexes are well known, 11,14 complexes featuring hypervalent tellurium species as ligands are extremely scarce and limited to tetravalent tellurium species.…”

Two-Electron Redox Chemistry at the Dinuclear Core of a TePt Platform: Chlorine Photoreductive Elimination and Isolation of a TeVPtI Complex

“…The presence of a Te–Pt bond is unambiguously confirmed by a Te-Pt bond distance of 2.5238(5) Å which is almost identical to that in [ 1 ] + (2.5281(5) Å). The short Te–F (1.954(2) Å), Te–O(1) (1.993(3) Å), and Te–O(2) (1.988(2) (2) Å) bonds are comparable to those observed for other hexavalent tellurium species with similar linkages (Te–F = 2.011 (2) Å in Ph 5 TeF, Te–O = 1.930(3) and 1.945(4) Å in (Ph 3 SnO) 2 Te­(OMe) 4 ) . To our knowledge, compound 4 is the first example of a hexavalent tellurium ligand in the coordination sphere of a metal.…”

“…The (2) Å) bonds are comparable to those observed for other hexavalent tellurium species with similar linkages (Te−F = 2.011 (2) Å in Ph 5 TeF, 24 Te−O = 1.930(3) and 1.945(4) Å in (Ph 3 SnO) 2 Te(OMe) 4 ). 27 To our knowledge, compound 4 is the first example of a hexavalent tellurium ligand in the coordination sphere of a metal. Indeed, while telluroether complexes are well known, 11,14 complexes featuring hypervalent tellurium species as ligands are extremely scarce and limited to tetravalent tellurium species.…”

Organotin(IV) Complexes Containing Sn–O–Se Moieties: A Structural Inventory

“…Tellurium-containing organo-oxotin derivatives, which also arouse growing interest, are not included in this inventory. However, to date, twenty-six X-ray crystallographic structures have been identified in the Cambridge Structural Database, which are mostly attributed to the four distinct research groups of Beckmann, 14 Ma, 15 Merzweiler 16 and Vij. 17 Regarding the selenium oxoanions, two types are known: (i) selenites (SeO 3 2-), and (ii) selenates (SeO 4 2-), which are differentiated by the oxidation state of selenium, +IV and +VI, respectively.…”

Two-Electron Redox Chemistry at the Dinuclear Core of a TePt Platform: Chlorine Photoreductive Elimination and Isolation of a TeVPtI Complex

“…The presence of a Te–Pt bond is unambiguously confirmed by a Te-Pt bond distance of 2.5238(5) Å which is almost identical to that in [ 1 ] + (2.5281(5) Å). The short Te–F (1.954(2) Å), Te–O(1) (1.993(3) Å), and Te–O(2) (1.988(2) (2) Å) bonds are comparable to those observed for other hexavalent tellurium species with similar linkages (Te–F = 2.011 (2) Å in Ph 5 TeF, Te–O = 1.930(3) and 1.945(4) Å in (Ph 3 SnO) 2 Te­(OMe) 4 ) . To our knowledge, compound 4 is the first example of a hexavalent tellurium ligand in the coordination sphere of a metal.…”

“…The (2) Å) bonds are comparable to those observed for other hexavalent tellurium species with similar linkages (Te−F = 2.011 (2) Å in Ph 5 TeF, 24 Te−O = 1.930(3) and 1.945(4) Å in (Ph 3 SnO) 2 Te(OMe) 4 ). 27 To our knowledge, compound 4 is the first example of a hexavalent tellurium ligand in the coordination sphere of a metal. Indeed, while telluroether complexes are well known, 11,14 complexes featuring hypervalent tellurium species as ligands are extremely scarce and limited to tetravalent tellurium species.…”

Organotin(IV) Complexes Containing Sn–O–Se Moieties: A Structural Inventory

“…Tellurium-containing organo-oxotin derivatives, which also arouse growing interest, are not included in this inventory. However, to date, twenty-six X-ray crystallographic structures have been identified in the Cambridge Structural Database, which are mostly attributed to the four distinct research groups of Beckmann, 14 Ma, 15 Merzweiler 16 and Vij. 17 Regarding the selenium oxoanions, two types are known: (i) selenites (SeO 3 2-), and (ii) selenates (SeO 4 2-), which are differentiated by the oxidation state of selenium, +IV and +VI, respectively.…”

Two-Electron Redox Chemistry at the Dinuclear Core of a TePt Platform: Chlorine Photoreductive Elimination and Isolation of a TeVPtI Complex

“…The presence of a Te–Pt bond is unambiguously confirmed by a Te-Pt bond distance of 2.5238(5) Å which is almost identical to that in [ 1 ] + (2.5281(5) Å). The short Te–F (1.954(2) Å), Te–O(1) (1.993(3) Å), and Te–O(2) (1.988(2) (2) Å) bonds are comparable to those observed for other hexavalent tellurium species with similar linkages (Te–F = 2.011 (2) Å in Ph 5 TeF, Te–O = 1.930(3) and 1.945(4) Å in (Ph 3 SnO) 2 Te­(OMe) 4 ) . To our knowledge, compound 4 is the first example of a hexavalent tellurium ligand in the coordination sphere of a metal.…”

“…The (2) Å) bonds are comparable to those observed for other hexavalent tellurium species with similar linkages (Te−F = 2.011 (2) Å in Ph 5 TeF, 24 Te−O = 1.930(3) and 1.945(4) Å in (Ph 3 SnO) 2 Te(OMe) 4 ). 27 To our knowledge, compound 4 is the first example of a hexavalent tellurium ligand in the coordination sphere of a metal. Indeed, while telluroether complexes are well known, 11,14 complexes featuring hypervalent tellurium species as ligands are extremely scarce and limited to tetravalent tellurium species.…”

Organotin(IV) Complexes Containing Sn–O–Se Moieties: A Structural Inventory

“…Tellurium-containing organo-oxotin derivatives, which also arouse growing interest, are not included in this inventory. However, to date, twenty-six X-ray crystallographic structures have been identified in the Cambridge Structural Database, which are mostly attributed to the four distinct research groups of Beckmann, 14 Ma, 15 Merzweiler 16 and Vij. 17 Regarding the selenium oxoanions, two types are known: (i) selenites (SeO 3 2-), and (ii) selenates (SeO 4 2-), which are differentiated by the oxidation state of selenium, +IV and +VI, respectively.…”