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