The reaction of [ReO(OEt)Cl-2(PPh3)(2)] with N-(2-pyridylmethyl)-2-aminoethanol (mpenOH) afforded a mixture of Re-V-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)Cl-2(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 (H(2)eg) was added to the mixture of [ReO(OEt)Cl-2(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)Cl-2(PPh3)(2)] with pyridylmethylamine derivatives (mpenOH and bpenOH) is discussed. Crystal data : [ReOCl2(mpenO)] (1), monoclinic, space group P2(1)/c, a = 8.632(1) Angstrom, b = 9.288(1) Angstrom, c = 14.802(1) Angstrom, beta = 100.627(9)degrees, Z = 4; [ReOCl(PPh2)(mpenO)](PF6). 0.5CH(3)CN), monoclinic, space group P2(1)/a, a = 19.758(6) Angstrom, b = 9.463(3) Angstrom, c = 16.297(4) Angstrom, beta = 93.40(2)degrees, Z = 4; [ReOCl2(bpenO)] (3), monoclinic, space group P2(1), a = 6.577(1) Angstrom, b = 13.269(2) Angstrom, c = 9.686(2) Angstrom, beta = 105.00(2)degrees, Z = 2; [ReOCl(bpenO)](PF6) (4), triclinic, space group , a = 6.766(1) Angstrom, b = 14.538(2) Angstrom, c = 19.373(3) Angstrom, alpha = 91.57(1)degrees, beta = 97.43(1)degrees, gamma = 91.62(1)degrees, Z = 4; [ReO(eg)(bpenOH)](ReO4) (5), monoclinic, space group P2(1)/n, a = 12.691(2) Angstrom, b = 14.030(2) Angstrom, c = 11.153(2) Angstrom, beta = 90.72(1)degrees, Z = 4.