Correia J D, Domingos A, Santos I, Alberto R, Ortner K
Departamento de Química, ITN, Estrada Nacional 10, 2686-953 Sacavém Codex, Portugal.
Inorg Chem. 2001 Sep 24;40(20):5147-51. doi: 10.1021/ic010417l.
The coordination chemistry of the heterofunctionalized phosphines HPN2 and H2PNO and of an analogue containing a relevant biomolecule, HPN-Pip (Pip = 4-(3-aminopropyl)-1-(2-methoxyphenyl)piperazine), was studied toward the synthon (NE4)2[ReBr3(CO)3]. The complexes isolated, [Re(CO)3(kappa(3)-PN2)], 3, [Re(CO)3Br(kappa(2)-H2PNO)], 4, and [Re(CO)3Br(kappa(2)-HPN-Pip)], 5, are the first examples of Re(I) compounds stabilized by such a combination of donor atoms. All of the compounds are neutral, but the phosphines, depending on the combination of atoms, act as monoanionic and tridentate (3) or as neutral and bidentate (4, 5). The characterization of 3-5 included IR, 1H NMR, and 31P NMR spectroscopy and X-ray crystallographic analysis. Colorless crystals of compounds 3 and 4 were obtained by slow evaporation of a methanolic solution of 3 and from a boiling acetonitrile solution of 4. Compound 3 crystallizes with two molecules of MeOH per asymmetric unit in the monoclinic space group P2(1)/c, a = 10.1237(8) A, b = 9.4959(4) A, c = 28.365(2) A, beta = 98.707(9) degrees, V = 2695.4(3) A(3), Z = 4; 4 crystallizes in the triclinic space group Ponebar, a = 10.0241(9) A, b = 11.2060(10) A, c = 13.0656(12) A, alpha = 84.883(11) degrees, beta = 71.163(10) degrees, gamma = 63.650(9) degrees, V = 1241.19(19) A(3), Z = 2.
研究了杂功能化膦HPN2、H2PNO以及一种含有相关生物分子的类似物HPN-Pip（Pip = 4-(3-氨丙基)-1-(2-甲氧基苯基)哌嗪）与合成子(NE4)2[ReBr3(CO)3]的配位化学。分离得到的配合物[Re(CO)3(κ(3)-PN2)]（3）、[Re(CO)3Br(κ(2)-H2PNO)]（4）和[Re(CO)3Br(κ(2)-HPN-Pip)]（5）是通过这种供体原子组合稳定的Re(I)化合物的首例。所有化合物均为中性，但膦根据原子组合的不同，可作为单阴离子三齿配体（3）或中性双齿配体（4、5）。对3至5的表征包括红外光谱、1H核磁共振谱和31P核磁共振谱以及X射线晶体学分析。化合物3和4的无色晶体分别通过3的甲醇溶液缓慢蒸发以及4的沸腾乙腈溶液获得。化合物3在单斜空间群P2(1)/c中结晶，每个不对称单元含有两个甲醇分子，a = 10.1237(8) Å，b = 9.4959(4) Å，c = 28.365(2) Å，β = 98.707(9)°，V = 2695.4(3) Å3，Z = 4；4在三斜空间群P1̅中结晶，a = 10.0241(9) Å，b = 11.2060(10) Å，c = 13.0656(12) Å，α = 84.883(11)°，β = 71.163(10)°，γ = 63.650(9)°，V = 1241.19(19) Å3，Z = 2。
