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Chelation Processes to an Oxorhenium(V) Center by N,N,N,O-Tetradentate and N,N,O-Tridentate Ligands As Verified by Structural and Mechanistic Studies of Intermediate Species
dataset
posted on 1998-03-03, 00:00 authored by J. Mattheus Botha, Keisuke Umakoshi, Yoichi Sasaki, Gert J. LamprechtThe reaction of
[ReO(OEt)Cl2(PPh3)2]
with N-(2-pyridylmethyl)-2-aminoethanol (mpenOH) afforded a
mixture
of ReV−oxo complexes, from which the dichloro complex
[ReOCl2(mpenO-N,N‘,O)]
(1) and the chlorotriphenylphosphine complex
[ReOCl(PPh3)(mpenO-N,N‘,O)]PF6
(2) were isolated by addition of
NH4PF6. Similarly,
[ReO(OEt)Cl2(PPh3)2]
reacted with
N,N-bis(2-pyridylmethyl)-2-aminoethanol
(bpenOH) to give the dichloro
complex
[ReOCl2(bpenO-N,N‘,O)]
(3) and the monochloro complex
[ReOCl(bpenO-N,N‘,N‘‘,O)]PF6
(4). When
ethylene glycol (H2eg) was added to the mixture of
[ReO(OEt)Cl2(PPh3)2]
and bpenOH, [ReO(eg)(bpenOH-N,N‘,N‘‘)]ReO4
(5) was obtained. These five newly prepared complexes
were structurally characterized. A
mechanistic insight into the stepwise complex formation reaction of
[ReO(OEt)Cl2(PPh3)2]
with pyridylmethylamine
derivatives (mpenOH and bpenOH) is discussed. Crystal data:
[ReOCl2(mpenO)] (1), monoclinic, space
group
P21/c, a = 8.632(1)
Å, b = 9.288(1) Å, c = 14.802(1)
Å, β = 100.627(9)°, Z = 4;
[ReOCl(PPh3)(mpenO)](PF6)·0.5CH3CN
(2·0.5CH3CN), monoclinic, space group
P21/a, a =
19.758(6) Å, b = 9.463(3)
Å, c = 16.297(4) Å, β = 93.40(2)°,
Z = 4; [ReOCl2(bpenO)] (3),
monoclinic, space group P21, a =
6.577(1) Å,
b = 13.269(2) Å, c = 9.686(2) Å,
β = 105.00(2)°, Z = 2;
[ReOCl(bpenO)](PF6) (4), triclinic,
space group P1̄,
a = 6.766(1) Å, b = 14.538(2) Å,
c = 19.373(3) Å, α = 91.57(1)°, β =
97.43(1)°, γ = 91.62(1)°, Z =
4;
[ReO(eg)(bpenOH)](ReO4) (5),
monoclinic, space group P21/n,
a = 12.691(2) Å, b = 14.030(2) Å,
c = 11.153(2) Å, β = 90.72(1)°, Z = 4.