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
J. Mattheus Botha
Keisuke Umakoshi
Yoichi Sasaki
Gert J. Lamprecht
10.1021/ic971477n.s001
https://acs.figshare.com/articles/dataset/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/3620970
The reaction of
[ReO(OEt)Cl<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub>]
with <i>N</i>-(2-pyridylmethyl)-2-aminoethanol (mpenOH) afforded a
mixture
of Re<sup>V</sup>−oxo complexes, from which the dichloro complex
[ReOCl<sub>2</sub>(mpenO-<i>N</i>,<i>N</i>‘,<i>O</i>)]
(<b>1</b>) and the chlorotriphenylphosphine complex
[ReOCl(PPh<sub>3</sub>)(mpenO-<i>N</i>,<i>N</i>‘,<i>O</i>)]PF<sub>6</sub>
(<b>2</b>) were isolated by addition of
NH<sub>4</sub>PF<sub>6</sub>. Similarly,
[ReO(OEt)Cl<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub>]
reacted with
<i>N</i>,<i>N</i>-bis(2-pyridylmethyl)-2-aminoethanol
(bpenOH) to give the dichloro
complex
[ReOCl<sub>2</sub>(bpenO-<i>N</i>,<i>N</i>‘,<i>O</i>)]
(<b>3</b>) and the monochloro complex
[ReOCl(bpenO-<i>N</i>,<i>N</i>‘,<i>N</i>‘‘,<i>O</i>)]PF<sub>6</sub>
(<b>4</b>). When
ethylene glycol (H<sub>2</sub>eg) was added to the mixture of
[ReO(OEt)Cl<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub>]
and bpenOH, [ReO(eg)(bpenOH-<i>N</i>,<i>N</i>‘,<i>N</i>‘‘)]ReO<sub>4</sub>
(<b>5</b>) was obtained. These five newly prepared complexes
were structurally characterized. A
mechanistic insight into the stepwise complex formation reaction of
[ReO(OEt)Cl<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub>]
with pyridylmethylamine
derivatives (mpenOH and bpenOH) is discussed. Crystal data:
[ReOCl<sub>2</sub>(mpenO)] (<b>1</b>), monoclinic, space
group
<i>P</i>2<sub>1</sub>/<i>c</i>, <i>a</i> = 8.632(1)
Å, <i>b</i> = 9.288(1) Å, <i>c</i> = 14.802(1)
Å, β = 100.627(9)°, <i>Z</i> = 4;
[ReOCl(PPh<sub>3</sub>)(mpenO)](PF<sub>6</sub>)·0.5CH<sub>3</sub>CN
(<b>2</b>·0.5CH<sub>3</sub>CN), monoclinic, space group
<i>P</i>2<sub>1</sub>/<i>a</i>, <i>a</i> =
19.758(6) Å, <i>b</i> = 9.463(3)
Å, <i>c</i> = 16.297(4) Å, β = 93.40(2)°,
<i>Z</i> = 4; [ReOCl<sub>2</sub>(bpenO)] (<b>3</b>),
monoclinic, space group <i>P</i>2<sub>1</sub>, <i>a</i> =
6.577(1) Å,
<i>b</i> = 13.269(2) Å, <i>c</i> = 9.686(2) Å,
β = 105.00(2)°, <i>Z</i> = 2;
[ReOCl(bpenO)](PF<sub>6</sub>) (<b>4</b>), triclinic,
space group <i>P</i>1̄,
<i>a</i> = 6.766(1) Å, <i>b</i> = 14.538(2) Å,
<i>c</i> = 19.373(3) Å, α = 91.57(1)°, β =
97.43(1)°, γ = 91.62(1)°, <i>Z</i> =
4;
[ReO(eg)(bpenOH)](ReO<sub>4</sub>) (<b>5</b>),
monoclinic, space group <i>P</i>2<sub>1</sub>/<i>n</i>,
<i>a</i> = 12.691(2) Å, <i>b</i> = 14.030(2) Å,
<i>c</i> = 11.153(2) Å, β = 90.72(1)°, <i>Z</i> = 4.
1998-03-03 00:00:00
ReOCl 2
PPh 3
NH 4 PF 6
bpenOH
H 2 eg
CH
space group P 2 1
CN
mpenO