Benny Paul D, Green Jenny L, Engelbrecht Hendrik P, Barnes Charles L, Jurisson Silvia S
Department of Chemistry, University of Missouri, 125 Chemistry Building, 601 S. College Avenue, Columbia, Missouri 65211, USA.
Inorg Chem. 2005 Apr 4;44(7):2381-90. doi: 10.1021/ic048670j.
The symmetric rhenium(V) oxo Schiff base complexes trans-[ReO(OH2)(acac2en)]Cl and trans-[ReOCl(acac2pn)], where acac2en and acac2pn are the tetradentate Schiff base ligands N,N'-ethylenebis(acetylacetone) diimine and N,N'-propylenebis(acetylacetone) diimine, respectively, were reacted with monodentate phosphine ligands to yield one of two unique cationic phosphine complexes depending on the ligand backbone length (en vs pn) and the identity of the phosphine ligand. Reduction of the Re(V) oxo core to Re(III) resulted on reaction of trans-[ReO(OH2)(acac2en)]Cl with triphenylphosphine or diethylphenylphosphine to yield a single reduced, disubstituted product of the general type trans-[Re(III)(PR3)2(acac2en)]+. Rather unexpectedly, a similar reaction with the stronger reducing agent triethylphosphine yielded the intramolecularly rearranged, asymmetric cis-[Re(V)O(PEt3)(acac2en)]+ complex. Reactions of trans-[Re(V)O(acac2pn)Cl] with the same phosphine ligands yielded only the rearranged asymmetric cis-[Re(V)O(PR3)(acac2pn)]+ complexes in quantitative yield. The compounds were characterized using standard spectroscopic methods, elemental analyses, cyclic voltammetry, and single-crystal X-ray diffraction. The crystallographic data for the structures reported are as follows: trans-[Re(III)(PPh3)2(acac2en)]PF6 (H48C48N2O2P2Re.PF6), 1, triclinic (P), a = 18.8261(12) A, b = 16.2517(10) A, c = 15.4556(10) A, alpha = 95.522(1) degrees , beta = 97.130(1) degrees , gamma = 91.350(1) degrees , V = 4667.4(5) A(3), Z = 4; trans-[Re(III)(PEt2Ph)2(acac2en)]PF6 (H48C32N2O2P2Re.PF6), 2, orthorhombic (Pccn), a = 10.4753(6) A, b =18.4315(10) A, c = 18.9245(11) A, V = 3653.9(4) A3, Z = 4; cis-[Re(V)O(PEt3)(acac2en)]PF6 (H33C18N2O3PRe.1.25PF6, 3, monoclinic (C2/c), a = 39.8194(15) A, b = 13.6187(5) A, c = 20.1777(8) A, beta = 107.7730(10) degrees , V = 10419.9(7) A3, Z = 16; cis-[Re(V)O(PPh3)(acac2pn)]PF6 (H35C31N2O3PRe.PF6), 4, triclinic (P), a = 10.3094(10) A, b =12.1196(12) A, c = 14.8146(15) A, alpha = 105.939(2) degrees , beta = 105.383(2) degrees , gamma = 93.525(2) degrees , V = 1698.0(3) A3, Z = 2; cis-[Re(V)O(PEt2Ph)(acac2pn)]PF6 (H35C23N2O3PRe.PF6), 5, monoclinic (P2(1)/n), a = 18.1183(18) A, b = 11.580(1) A, c = 28.519(3) A, beta = 101.861(2) degrees , V = 5855.9(10) A(3), Z = 4.
对称的铼（V）氧代席夫碱配合物反式-[ReO(OH₂)(acac₂en)]Cl和反式-[ReOCl(acac₂pn)]，其中acac₂en和acac₂pn分别是四齿席夫碱配体N,N'-亚乙基双（乙酰丙酮）二亚胺和N,N'-亚丙基双（乙酰丙酮）二亚胺，它们与单齿膦配体反应，根据配体主链长度（en对pn）和膦配体的特性生成两种独特的阳离子膦配合物之一。反式-[ReO(OH₂)(acac₂en)]Cl与三苯基膦或二乙苯基膦反应，使Re(V)氧代核心还原为Re(III)，生成通式为反式-[Re(III)(PR₃)₂(acac₂en)]⁺的单一还原、双取代产物。相当出乎意料的是，与更强的还原剂三乙膦进行类似反应，生成了分子内重排的不对称顺式-[Re(V)O(PEt₃)(acac₂en)]⁺配合物。反式-[Re(V)O(acac₂pn)Cl]与相同的膦配体反应，仅以定量产率生成重排的不对称顺式-[Re(V)O(PR₃)(acac₂pn)]⁺配合物。使用标准光谱方法、元素分析、循环伏安法和单晶X射线衍射对这些化合物进行了表征。所报道结构的晶体学数据如下：反式-[Re(III)(PPh₃)₂(acac₂en)]PF₆（H₄₈C₄₈N₂O₂P₂Re.PF₆），1，三斜晶系（P），a = 18.8261(12) Å，b = 16.2517(10) Å，c = 15.4556(10) Å，α = 95.522(1)°，β = 97.130(1)°，γ = 91.350(1)°，V = 4667.4(5) ų，Z = 4；反式-[Re(III)(PEt₂Ph)₂(acac₂en)]PF₆（H₄₈C₃₂N₂O₂P₂Re.PF₆），2，正交晶系（Pccn），a = 10.4753(6) Å，b =18.4315(10) Å，c = 18.9245(11) Å，V = 3653.9(4) ų，Z = 4；顺式-[Re(V)O(PEt₃)(acac₂en)]PF₆（H₃₃C₁₈N₂O₃PRe.1.25PF₆，3，单斜晶系（C2/c），a = 39.8194(15) Å，b = 13.6187(5) Å，c = 20.1777(8) Å，β = 107.7730(10)°，V = 10419.9(7) ų，Z = 16；顺式-[Re(V)O(PPh₃)(acac₂pn)]PF₆（H₃₅C₃₁N₂O₃PRe.PF₆），4，三斜晶系（P），a = 10.3094(10) Å，b =12.1196(12) Å，c = 14.8146(15) Å，α = 105.939(2)°，β = 105.383(2)°，γ = 93.525(2)°，V = 1698.0(3) ų，Z = 2；顺式-[Re(V)O(PEt₂Ph)(acac₂pn)]PF₆（H₃₅C₂₃N₂O₃PRe.PF₆），5，单斜晶系（P2(1)/n），a = 18.1183(18) Å，b = 11.580(1) Å，c = 28.519(3) Å，β = 101.861(2)°，V = 5855.9(10) ų，Z = 4。
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