Syntheses and structural characterization of tetrahedral four-coordinate gold(I) complexes of 1,3,5-triaza-7-phosphaadamantane. An example of a hydrogen-bond-directed supramolecular assembly
Syntheses and structural characterization of tetrahedral four-coordinate gold(I) complexes of 1,3,5-triaza-7-phosphaadamantane. An example of a hydrogen-bond-directed supramolecular assembly
复制标题
DOI：
10.1021/ic950560c
复制
发表时间：
1996-01-03
影响因子：
4.6
通讯作者：
Fackler, JP
中科院分区：
文献类型：
--
作者：
Forward, JM;Assefa, Z;Fackler, JP
本文报道了含单齿膦配体的水溶性四配位金配合物的合成和结构表征。使用的配体是1，3，5-三氮杂-7-磷杂金刚烷（TPA）及其质子化和甲基化衍生物，[HTPA]Cl和[MeTPA]I。四配位金（I）物种的形成受到膦的小锥角（102度）及其在配体的氮原子和溶剂水分子之间形成氢键网络的能力的促进。在所有四个配合物中的金中心具有几乎规则的四面体几何形状，平均P-Au-P角为109.5度。[（HTPA）（3）（TPA）Au]（PF 6）（4）。4H（2）O . CH 3 CN（1）在单斜空间群P2（1）/c（No.14）中结晶，晶胞常数a = 20.719（3）埃，B = 15.606（2）埃，c = 17.854（2）埃，β = 114.03（1）度，Z = 4。对4977个反射和650个参数的细化产生R = 0.0396和R（w）= 0.0500。[（TPA）（4）Au] PF 6. 1.5盐酸。H2O（2），以单斜空间群C2/c（No.15）结晶，晶胞常数a = 33.036（7）埃，B = 11.212（2）埃，c = 31.503（5）埃，B = 137.58（1）度和Z = 8。对3835个反射和470个参数的细化产生R = 0.0351和R（w）= 0.0403。[（TPA）（4）Au]Cl-4。6 H（2）O（3）的结构特征为立方空间群Fd（3），在bar m（No.227）上，晶胞常数a = B = c = 20.020（2）埃，Z = 8。对290个反射和28个参数进行细化，得到R = 0.0624和R（w）= 0.1291。[（MeTPA）（4）Au]（PF 6）（5）。2CH（3）CN（4）以单斜空间群C2/c（No.15）结晶，具有晶胞，常数a = 23.337（3）埃，B = 14.855（3）埃，c = 35.317（5）埃，B = 97.95（1）度，Z = 8。对7840个反射和621个参数进行细化，得到R = 0.0493和R（w）= 0.0698。
The synthesis and structural characterization of water-soluble four-coordinate gold(I) complexes containing monodentate phosphine ligands are described. The ligands used are 1,3,5-triaza-7-phosphaadamantane (TPA) and its protonated and methylated derivatives, [HTPA]Cl and [MeTPA]I. Formation of the four-coordinate gold(I) species is favored by the small cone angle of the phosphine (102 degrees) and its ability to form a hydrogen-bonded network between the nitrogen atoms of the ligand and solvent water molecules. The gold center in all four complexes has a nearly regular tetrahedral geometry with an average P-Au-P angle of 109.5 degrees. [(HTPA)(3)(TPA)Au](PF6)(4) . 4H(2)O . CH3CN (1) crystallizes in the monoclinic space group P2(1)/c (No. 14) with cell constants a = 20.719(3) Angstrom, b = 15.606(2) Angstrom, c = 17.854(2) Angstrom, beta = 114.03(1)degrees, and Z = 4. Refinement of 4977 reflections and 650 parameters yields R = 0.0396 and R(w) = 0.0500. [(TPA)(4)Au]PF6 . 1.5HCl . H2O (2), crystallizes in the monoclinic space group C2/c (No. 15) with cell constants a = 33.036(7) Angstrom, b = 11.212(2) Angstrom, c = 31.503(5) Angstrom, b = 137.58(1)degrees and Z = 8. Refinement of 3835 reflections and 470 parameters yields R = 0.0351 and R(w) = 0.0403. [(TPA)(4)Au]Cl-4 . 6H(2)O (3) was characterized structurally in the cubic space group Fd (3) over bar m (No. 227) with cell constants a = b = c = 20.020(2) Angstrom and Z = 8. Refinement of 290 reflections and 28 parameters yields R = 0.0624 and R(w) = 0.1291. [(MeTPA)(4)Au](PF6)(5) . 2CH(3)CN (4) crystallizes in the monoclinic space group C2/c (No. 15) with cell, constants a = 23.337(3) Angstrom, b = 14.855(3) Angstrom, c = 35.317(5) Angstrom, b = 97.95(1)degrees, and Z = 8. Refinement of 7840 reflections and 621 parameters yields R = 0.0493 and R(w) = 0.0698.