TY - JOUR
T1 - Rhenium(I) carbonyl complexes of 2,4,6-tris(2-pyridyl)-1,3,5-triazine (TPT). Rhenium(I)-promoted methoxylation of the triazine ring carbon atom in dinuclear rhenium complexes
AU - Chen, X.
AU - Femia, F. J.
AU - Babich, J. W.
AU - Zubieta, J. A.
PY - 2001/6/4
Y1 - 2001/6/4
N2 - 2,4,6-Tris(2-pyridyl)-1,3,5-triazine (TPT) bridged dinuclear rhenium(I) tricarbonyl halide complexes with the composition (μ-TPT)[ReX(CO)3]2 (3, X = Cl; 4, X = Br) can be made either by one-pot reaction of TPT with 2 equiv of [ReX(CO)5] (X = Cl and Br) in chloroform or by reacting mononuclear [ReX(CO)3(TPT)]2 (1, X = Cl; 2, X = Br) with an excess amount of [ReX(CO)5]. Crystal data are as follows. 1:. monoclinic, P21/c, a = 11.751(1) Å, b = 11.376(1) Å, c = 15.562(2) Å, β = 103.584(2)°, V = 2022.0(4) Å3, Z = 4. 2: monoclinic, P21/c, a = 11.896(1) Å, b = 11.396(1) Å, c =15.655(1) Å, β 104.474(2)°, V = 2054.9(3) Å3, Z = 4. 3: triclinic, P1, a = 11.541(2) Å, b = 12.119(2) Å, c = 13.199(2) Å, α = 80.377(2)°, β = 76.204(3)°, γ = 66.826(2)°, V = 1642.5(4) Å3, Z = 2. Crystals of 4 crystallized from acetone: triclinic, P1, a = 11.586(5) Å, b = 12.144(5) Å, c = 13.364(6) Å, α = 80.599(7)°, β = 76.271(8)°, γ = 67.158(8)°, V = 1678.0(12) Å3, Z = 2. Crystals of 4′ are obtained from CH2Cl2-pentane solution: monoclinic, C2/c, a = 17.555(4) Å, b = 15.277(3) Å, c = 13.093(3) Å, β = 111.179(3)°, V = 3274.0(12) Å3, Z = 4. By contrast, similar reactions in the presence of methanol yielded complexes with the composition [μ-(C3N3(OMe)(py)]2[pyH)][(ReX) (CO)3]2 (5, X = Cl; 6, X = Br). Crystal data for 5: monoclinic, C2/c, a = 26.952(2) Å, b = 16.602(1) Å, c = 14.641(1) Å, β= 116.147(1)°, V = 5880.5(8) Å3, Z = 8. 6: monoclinic, C2/c, a = 27.513(3) Å, b = 16.740(2), Å, c = 14.837(2) Å, 14.837(2) Å, β = 116.925(2)°, V = 5880.5(8) Å3, Z = 8. 6: monoclinic, C2/c, a = 27.513(3) Å, b = 16.740(2) Å, c = 14.837(2) Å, β = 116.925(2)°, V = 6092.8(10) Å3, Z = 8. An unusual metal-induced methoxylation at the carbon atom of the triazine ring of the bridging TPT ligand was observed. The nucleophilic attack of MeO- on C(3) results in a tetrahedral geometry around the carbon atom. Concomitantly, the uncoordinated pyridyl ring is protonated and rotated into a perpendicular orientation relative to the central C3N3 ring. Reaction of TPT with [NEt4]2[ReBr3(CO)3] in benzene -methanol resulted in an unexpected dinuclear complex 7, with formulation [μ-C3N3(OMe)(py)3][Re(CO)3] [ReBr(CO)3]. The methoxylated TPT ligand functions simultaneously as a tridentate and bidentate ligand with two fac-Re(CO)3+ cores. Crystal data for 7: monoclinic, P21/n, a = 12.114(1) Å, b = 14.878(1) Å, c = 15.807(1) Å β = 104.601(1)°, V = 2756.9(3) Å3, Z = 4.
AB - 2,4,6-Tris(2-pyridyl)-1,3,5-triazine (TPT) bridged dinuclear rhenium(I) tricarbonyl halide complexes with the composition (μ-TPT)[ReX(CO)3]2 (3, X = Cl; 4, X = Br) can be made either by one-pot reaction of TPT with 2 equiv of [ReX(CO)5] (X = Cl and Br) in chloroform or by reacting mononuclear [ReX(CO)3(TPT)]2 (1, X = Cl; 2, X = Br) with an excess amount of [ReX(CO)5]. Crystal data are as follows. 1:. monoclinic, P21/c, a = 11.751(1) Å, b = 11.376(1) Å, c = 15.562(2) Å, β = 103.584(2)°, V = 2022.0(4) Å3, Z = 4. 2: monoclinic, P21/c, a = 11.896(1) Å, b = 11.396(1) Å, c =15.655(1) Å, β 104.474(2)°, V = 2054.9(3) Å3, Z = 4. 3: triclinic, P1, a = 11.541(2) Å, b = 12.119(2) Å, c = 13.199(2) Å, α = 80.377(2)°, β = 76.204(3)°, γ = 66.826(2)°, V = 1642.5(4) Å3, Z = 2. Crystals of 4 crystallized from acetone: triclinic, P1, a = 11.586(5) Å, b = 12.144(5) Å, c = 13.364(6) Å, α = 80.599(7)°, β = 76.271(8)°, γ = 67.158(8)°, V = 1678.0(12) Å3, Z = 2. Crystals of 4′ are obtained from CH2Cl2-pentane solution: monoclinic, C2/c, a = 17.555(4) Å, b = 15.277(3) Å, c = 13.093(3) Å, β = 111.179(3)°, V = 3274.0(12) Å3, Z = 4. By contrast, similar reactions in the presence of methanol yielded complexes with the composition [μ-(C3N3(OMe)(py)]2[pyH)][(ReX) (CO)3]2 (5, X = Cl; 6, X = Br). Crystal data for 5: monoclinic, C2/c, a = 26.952(2) Å, b = 16.602(1) Å, c = 14.641(1) Å, β= 116.147(1)°, V = 5880.5(8) Å3, Z = 8. 6: monoclinic, C2/c, a = 27.513(3) Å, b = 16.740(2), Å, c = 14.837(2) Å, 14.837(2) Å, β = 116.925(2)°, V = 5880.5(8) Å3, Z = 8. 6: monoclinic, C2/c, a = 27.513(3) Å, b = 16.740(2) Å, c = 14.837(2) Å, β = 116.925(2)°, V = 6092.8(10) Å3, Z = 8. An unusual metal-induced methoxylation at the carbon atom of the triazine ring of the bridging TPT ligand was observed. The nucleophilic attack of MeO- on C(3) results in a tetrahedral geometry around the carbon atom. Concomitantly, the uncoordinated pyridyl ring is protonated and rotated into a perpendicular orientation relative to the central C3N3 ring. Reaction of TPT with [NEt4]2[ReBr3(CO)3] in benzene -methanol resulted in an unexpected dinuclear complex 7, with formulation [μ-C3N3(OMe)(py)3][Re(CO)3] [ReBr(CO)3]. The methoxylated TPT ligand functions simultaneously as a tridentate and bidentate ligand with two fac-Re(CO)3+ cores. Crystal data for 7: monoclinic, P21/n, a = 12.114(1) Å, b = 14.878(1) Å, c = 15.807(1) Å β = 104.601(1)°, V = 2756.9(3) Å3, Z = 4.
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U2 - 10.1021/ic000446g
DO - 10.1021/ic000446g
M3 - Article
C2 - 11375694
AN - SCOPUS:0035805670
SN - 0020-1669
VL - 40
SP - 2769
EP - 2777
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 12
ER -