Reactivity of Rhenium(V) Oxo Schiff Base Complexes with Phosphine Ligands: Rearrangement and Reduction Reactions
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- 作者：Paul D. Benny ; Jenny L. Green ; Hendrik P. Engelbrecht ; Charles L. Barnes ; and Silvia S. Jurisson
- 刊名：Inorganic Chemistry
- 出版年：2005
- 出版时间：April 4, 2005
- 年：2005
- 卷：44
- 期：7
- 页码：2381 - 2390
- 全文大小：217K
- 年卷期：v.44,no.7(April 4, 2005)
- ISSN：1520-510X
文摘
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 andN,N'-propylenebis(acetylacetone) diimine, respectively, were reacted with monodentate phosphine ligands to yieldone of two unique cationic phosphine complexes depending on the ligand backbone length (en vs pn) and theidentity 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 productof the general type trans-[ReIII(PR3)2(acac2en)]+. Rather unexpectedly, a similar reaction with the stronger reducingagent triethylphosphine yielded the intramolecularly rearranged, asymmetric cis-[ReVO(PEt3)(acac2en)]+ complex.Reactions of trans-[ReVO(acac2pn)Cl] with the same phosphine ligands yielded only the rearranged asymmetriccis-[ReVO(PR3)(acac2pn)]+ complexes in quantitative yield. The compounds were characterized using standardspectroscopic methods, elemental analyses, cyclic voltammetry, and single-crystal X-ray diffraction. Thecrystallographic data for the structures reported are as follows: trans-[ReIII(PPh3)2(acac2en)]PF6 (H48C48N2O2P2Re·PF6), 1, triclinic (P
), a = 18.8261(12) Å, b = 16.2517(10) Å, c = 15.4556(10) Å, 
= 95.522(1)
, 
beta2.gif" BORDER=0 ALIGN="middle"> =97.130(1), 
= 91.350(1), V = 4667.4(5) Å3, Z = 4; trans-[ReIII(PEt2Ph)2(acac2en)]PF6 (H48C32N2O2P2Re·PF6),2, orthorhombic (Pccn), a = 10.4753(6) Å, b =18.4315(10) Å, c = 18.9245(11) Å, V = 3653.9(4) Å3, Z = 4;cis-[ReVO(PEt3)(acac2en)]PF6 (H33C18N2O3PRe·1.25PF6), 3, monoclinic (C2/c), a = 39.8194(15) Å, b = 13.6187(5)Å, c = 20.1777(8) Å, beta2.gif" BORDER=0 ALIGN="middle"> = 107.7730(10), V = 10419.9(7) Å3, Z = 16; cis-[ReVO(PPh3)(acac2pn)]PF6 (H35C31N2O3PRe·PF6), 4, triclinic (P), a = 10.3094(10) Å, b =12.1196(12) Å, c = 14.8146(15) Å, = 105.939(2), beta2.gif" BORDER=0 ALIGN="middle"> =105.383(2), = 93.525(2), V = 1698.0(3) Å3, Z = 2; cis-[ReVO(PEt2Ph)(acac2pn)]PF6 (H35C23N2O3PRe·PF6), 5,monoclinic (P21/n), a = 18.1183(18) Å, b = 11.580(1) Å, c = 28.519(3) Å, beta2.gif" BORDER=0 ALIGN="middle"> = 101.861(2), V = 5855.9(10) Å3,Z = 4.
), a = 18.8261(12) Å, b = 16.2517(10) Å, c = 15.4556(10) Å, = 95.522(1), beta2.gif" BORDER=0 ALIGN="middle"> =97.130(1), = 91.350(1), V = 4667.4(5) Å3, Z = 4; trans-[ReIII(PEt2Ph)2(acac2en)]PF6 (H48C32N2O2P2Re·PF6),2, orthorhombic (Pccn), a = 10.4753(6) Å, b =18.4315(10) Å, c = 18.9245(11) Å, V = 3653.9(4) Å3, Z = 4;cis-[ReVO(PEt3)(acac2en)]PF6 (H33C18N2O3PRe·1.25PF6), 3, monoclinic (C2/c), a = 39.8194(15) Å, b = 13.6187(5)Å, c = 20.1777(8) Å, beta2.gif" BORDER=0 ALIGN="middle"> = 107.7730(10), V = 10419.9(7) Å3, Z = 16; cis-[ReVO(PPh3)(acac2pn)]PF6 (H35C31N2O3PRe·PF6), 4, triclinic (P), a = 10.3094(10) Å, b =12.1196(12) Å, c = 14.8146(15) Å, = 105.939(2), beta2.gif" BORDER=0 ALIGN="middle"> =105.383(2), = 93.525(2), V = 1698.0(3) Å3, Z = 2; cis-[ReVO(PEt2Ph)(acac2pn)]PF6 (H35C23N2O3PRe·PF6), 5,monoclinic (P21/n), a = 18.1183(18) Å, b = 11.580(1) Å, c = 28.519(3) Å, beta2.gif" BORDER=0 ALIGN="middle"> = 101.861(2), V = 5855.9(10) Å3,Z = 4.