TY - JOUR
T1 - Reactivity of rhenium(V) oxo Schiff base complexes with phosphine ligands
T2 - Rearrangement and reduction reactions
AU - Benny, Paul D.
AU - Green, Jenny L.
AU - Engelbrecht, Hendrik P.
AU - Barnes, Charles L.
AU - Jurisson, Silvia S.
PY - 2005/4/7
Y1 - 2005/4/7
N2 - The symmetric rhenium(V) oxo Schiff base complexes frans-[ReO(OH 2)(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 frans-[ReO-(OH2)(acac2en)]Cl with triphenylphosphine or diethylphenylphosphine to yield a single reduced, disubstituted product of the general type trans-[ReIII(PR 3)2(acac2en)]+. Rather unexpectedly, a similar reaction with the stronger reducing agent triethylphosphine yielded the intramolecularly rearranged, asymmetric cis-[ReVO(PEt 3)(acac2en)]+ complex. Reactions of frans-[RevO(acac2pn)CI] with the same phosphine ligands yielded only the rearranged asymmetric cis-[ReVO(PR3)(acac 2pn)]+ 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: frans-[ReIII(PPh 3)2(acac2en)]PF6 (H 48C48N2O2P3- Re·PF6), 1, triclinic (P1), 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) Å3, Z = 4; trans-[ReIII(PEt2Ph)2(acac 2en)]PF6 (H48C32N2O 2P2Re·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(PEt 3)(acac2en)]PF6 (H33C 18N2O3PRe·1.25PF6), 3, monoclinic (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) Å3, Z = 16; cis-[ReVO(PPh3)(acac 2pn)]PF6 (H35C31N2O 3-PRe·PF6), 4, triclinic (P1), 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) Å3, Z = 2; cis-[ReVO(PEt 2Ph)(acac2pn)]PF6 (H35C 23N2O3PRe·PF6), 5, monoclinic (P21/n), a = 18.1183(18) Å, b = 11.580(1) Å, c = 28.519(3) Å, β = 101.861(2)°, V = 5855.9(10) Å3, Z = 4.
AB - The symmetric rhenium(V) oxo Schiff base complexes frans-[ReO(OH 2)(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 frans-[ReO-(OH2)(acac2en)]Cl with triphenylphosphine or diethylphenylphosphine to yield a single reduced, disubstituted product of the general type trans-[ReIII(PR 3)2(acac2en)]+. Rather unexpectedly, a similar reaction with the stronger reducing agent triethylphosphine yielded the intramolecularly rearranged, asymmetric cis-[ReVO(PEt 3)(acac2en)]+ complex. Reactions of frans-[RevO(acac2pn)CI] with the same phosphine ligands yielded only the rearranged asymmetric cis-[ReVO(PR3)(acac 2pn)]+ 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: frans-[ReIII(PPh 3)2(acac2en)]PF6 (H 48C48N2O2P3- Re·PF6), 1, triclinic (P1), 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) Å3, Z = 4; trans-[ReIII(PEt2Ph)2(acac 2en)]PF6 (H48C32N2O 2P2Re·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(PEt 3)(acac2en)]PF6 (H33C 18N2O3PRe·1.25PF6), 3, monoclinic (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) Å3, Z = 16; cis-[ReVO(PPh3)(acac 2pn)]PF6 (H35C31N2O 3-PRe·PF6), 4, triclinic (P1), 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) Å3, Z = 2; cis-[ReVO(PEt 2Ph)(acac2pn)]PF6 (H35C 23N2O3PRe·PF6), 5, monoclinic (P21/n), a = 18.1183(18) Å, b = 11.580(1) Å, c = 28.519(3) Å, β = 101.861(2)°, V = 5855.9(10) Å3, Z = 4.
UR - http://www.scopus.com/inward/record.url?scp=16344394232&partnerID=8YFLogxK
U2 - 10.1021/ic048670j
DO - 10.1021/ic048670j
M3 - Article
AN - SCOPUS:16344394232
SN - 0020-1669
VL - 44
SP - 2381
EP - 2390
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 7
ER -