Synthesis, Characterization, and Stereochemistry of Oxorhenium(V) Complexes with 2-Aminoethanethiolate

A series of oxorhenium(V) complexes with 2-aminoethanethiolate (aet), [ReO(aet-N,S)(d-pen-N,O,S)] (2), [{ReO(aet-N,S)2}2O] (3), [ReO(Cl)(aet-N,S)2] (4), and [ReO(aet-N,S)(Haet-S)2]Cl2 ([5]Cl2) was newly prepared starting
from ReO4-. The reaction of NH4ReO4 with a 1:1 mixture of Haet·HCl and d-H2pen (d-penicillamine) in the
presence of SnCl2·2H2O in water gave 2, 3, and the known complex [ReO(d-Hpen-N,S)(d-pen-N,O,S)] (1). These
complexes were fractionally precipitated by controlling the pH of the reaction solution. The complex 2 was also
prepared in a higher yield by a similar reaction using methanol as a solvent. The crystal structure of 2 was
determined by X-ray crystallography; 2 crystallizes in the tetragonal space group P43 with a = 9.621(1), c =
12.911(1) Å, V = 1195.0(3) Å3, and Z = 4. The oxorhenium(V) core in 2 is coordinated by a bidentate-N,S aet
ligand and a tridentate-N,O,S d-pen ligand, having a distorted octahedral geometry with a cis-N cis-S configuration
in the equatorial plane perpendicular to the O−Re−O axis. The 1:2 reaction of NH4ReO4 with Haet·HCl in the
presence of SnCl2·2H2O in methanol produced 4, which is interconvertible with 3, while the corresponding 1:3
reaction resulted in the isolation of [5]Cl2. The complexes 4 and 5 were also structurally characterized; 4 crystallizes
in the monoclinic space group P21/c with a = 6.839(1), b = 10.0704(6), c = 14.1075(8) Å, β = 91.729(8)°, V
= 971.2(2) Å3, and Z = 4, while [5]Cl2 crystallizes in the triclinic space group P1̄ with a = 11.938(3), b =
12.366(3), c = 5.819(1) Å, α = 102.71(2), β = 101.28(2), γ = 75.41(2)°, V = 802.0(3) Å3, and Z = 2. In 4, the
oxorhenium(V) core is octahedrally coordinated by two bidentate-N,S aet ligands, which form a cis-N cis-S
configurational equatorial plane with a Cl- ion trans to the oxo ligand. On the other hand, the oxorhenium(V)
core in [5]2+ is coordinated by one bidenate-N,S aet and two monodentate-S Haet ligands, having a distorted
trigonal-bipyramidal geometry with S and N donors at the apical positions.

一系列由氧化铑(V)与2-氨基乙硫醇酯（aet）形成的复合物，包括[ReO(aet-N,S)(d-pen-N,O,S)](2)、[{ReO(aet-N,S)2}2O](3)、[ReO(Cl)(aet-N,S)2](4)以及[ReO(aet-N,S)(Haet-S)2]Cl2([5]Cl2)，均由ReO4-出发新合成制备。通过在水溶液中NH4ReO4与Haet·HCl和d-H2pen（d-青霉胺）的1:1混合物反应，并在SnCl2·2H2O的存在下，得到了2、3以及已知的复合物[ReO(d-Hpen-N,S)(d-pen-N,O,S)](1)。这些复合物通过调节反应溶液的pH值进行分步沉淀。复合物2还通过使用甲醇作为溶剂的类似反应以更高的产率制备。复合物2的晶体结构通过X射线晶体学确定；2以四方晶系P43空间群结晶，其晶胞参数为a = 9.621(1)、c = 12.911(1) Å，V = 1195.0(3) Å3，Z = 4。在复合物2中，氧化铑(V)核由一个双齿-N,S aet配体和一个三齿-N,O,S d-pen配体配位，呈现扭曲的八面体几何形状，在垂直于O−Re−O轴的赤道平面上具有顺式-N顺式-S构型。在甲醇中，NH4ReO4与Haet·HCl的1:2反应，并在SnCl2·2H2O的存在下，产生了4，该复合物与3可相互转化，而相应的1:3反应则导致了[5]Cl2的分离。复合物4和5的结构也得到了表征；4以单斜晶系P21/c空间群结晶，其晶胞参数为a = 6.839(1)、b = 10.0704(6)、c = 14.1075(8) Å，β = 91.729(8)°，V = 971.2(2) Å3，Z = 4，而[5]Cl2以三斜晶系P1空间群结晶，其晶胞参数为a = 11.938(3)、b = 12.366(3)、c = 5.819(1) Å，α = 102.71(2)、β = 101.28(2)、γ = 75.41(2)°，V = 802.0(3) Å3，Z = 2。在4中，氧化铑(V)核由两个双齿-N,S aet配位，这些配体与一个Cl-离子形成顺式-N顺式-S构型的赤道平面，该Cl-离子位于氧配体对面。另一方面，[5]2+中的氧化铑(V)核由一个双齿-N,S aet和两个单齿-S Haet配位，具有扭曲的三角双锥几何形状，顶点位置具有S和N供体。