Coordinated Three-Centered Bond: Synthesis and Structure Characterization of the N, N'-bis (4-tolylsulfonyl)-pyridine-2,6-diaminato Ligand and Its Dinuclear Ag (I), Cu (l) Metal Complexes

配位三中心鍵：2,6-二磺醯胺吡啶配基及其雙核銀（I）、銅（I）金屬錯合物的合成及鑑定

蔡明蒔(Ming-Shih Tsai) ； 彭旭明(Shie-Ming Peng)

《中央研究院化學研究所集刊》 42期 (1995/03) Pp. 63-73

https://doi.org/10.6522/BICAS.1995.42.8

摘要

2,6-二磺醯胺吡啶（Lpts^(2-) & Lms(2-)）雙核銀（I）、銅（I）金屬錯合物的合成及其單晶結構。無色之自由配基雙聚物［(Lpts)_2H_3][N(Bu)_4］之空間群為C 2/c，室元參數a = 27.124（3）Å，b = 10.462（4）Å，c = 20.316（2）Å，β = 99.48 （1）°，Z = 4，2356個繞射點之誤差指數為R = 0.068，Rw = 0.063。其結構為半脫除質子之配基藉由三對氫鍵形成二聚物，二配基平面間並非共平面，其扭轉角度約為40°。無色的［Ag(Lpts)_2］［N(Bu)_4］_2之空間群為P 2_1/c，室元參數：a = 19.094（4）Å，b = 17.579（6）Å，c = 23.084（5）Å，β = 99.76（2）°，Z = 4，4398個繞射點之誤差指數為R = 0.076，Rw = 0.072。兩陰性配基藉由胺基氮咬合兩銀離子形成一扭曲線形配位之12員雙金屬環錯合物。吡啶上氮原子微弱配位於此一銀離子形成配位三位中心鍵。無色之［Ag_2(Lpts)_2］［Net_3H］_2錯合物之空間群為P1，室元參數：a = 9.442（1）Å，b = 12.125（3）Å，c = 13.054（2）Å，α = 98.18（2）°，β= 72.05（1）°，γ = 91.87（2）° Z = 1, 1665個繞射點之誤差指數為R = 0.082，Rw = 0.093 。兩陰性配基咬合雙銀離子形成具線形配位之12員雙金屬環錯合物。雙銅錯合物［Cu_2（Lms）（NP）_2］可形成兩種不同構形的晶體，於二氯甲烷溶劑中，可得橙色之［Cu_2（Lms）（NP）_2］晶體，其空間群為Pna2_1，室元參數：a = 21.166（4）Å，b = 10.096（3）Å，c = 19.397（5）Å，Z = 4，2703個繞射點之誤差指數為R = 0.032，Rw = 0.031。於甲醇溶劑中，可得黃色之［Cu_2（Lms）（NP）_2]。MeOH晶體，其空間群為P 2_1/c，室元參數：a = 10.531(2)，b = 22.049(6)，c = 18.27(4)Å，β= 98.02(2)°，Z = 4，4328個繞射點之誤差指數為R = 0.052，Rw = 0.051。兩者結構類似，但黃色晶體為一配位三中心鍵結構，而橙色晶體結構則否。

並列摘要

Binuclear complexes of Ag (l) and Cu (l) metal ions, N, N'-bis (4-tolylsulfonyl)-pyridine- 2, 6-diaminato ligand (Lpts^(2-)), were isolated and the crystal structures determined with xray diffraction. The colorless hemi-deprotonated ligand of [N(Bu)_4][(Lpts)_2H_3] crystallized in the monoclinic space group C 2/c with a = 27.124 (3) Å, b = 10.462 (4) Å, c = 20.316(2)A, β = 99.48 (1) °, R = 0.068, R_w = 0.063 for 2356 observed reflections. The two hemi-deprotonated ligands form a dimer through three pairs of hydrogen bonds and are not co-planar, the twist angle is about 40°. The colorless compound [N(Bu)_4]_2[Ag_2(Lpts)_2] crystallized in the monoclinic space group P 2_1/c with a = 19.094 (4) Å, b = 17.579 (6) Å, c = 23.084 (5) Å, β = 99.76 (2)°, Z = 4, R = 0.076, Rw = 0.072 for 4398 observed reflections. The two dianionic ligands bind two silver (l) ions through amido nitrogen atoms in a distorted linear geometry forming a 12-membered dimetallocycle. The pyridine nitrogen atom is weakly coordinated to two silver(l) ions forming a coordinated three-centered bond . For comparison , the colorless compound [Net_3H]_2[Ag_2(Lbpts)_2] was synthesized and crystallized in the triclinic space group P1 with a = 9.442 (1) Å, b = 12.125 (3) Å, c = 13.054 (2) Å , α = 98.18 (2)°, β =72.05 (1)°, γ =91.87 (2)°, Z=1, R = 0.082, R_w = 0.093 for 1665 observed reflections. The two dian ionic ligands bind two silver (l) ions in a linear geometry forming a 12-membered dimetallocycle. The copper compound [Cu_2(Lms)(NP)_2] (Lms=N ,N'-bis(4-methylsulfonyl)pyridine-2, 6-diaminato, NP=2-(diphenylphosphino)pyridine) crystallized in two forms. From dichloromethane, orange crystals of [Cu_2(Lms)(NP)_2] were obtained in the orthorhombic space group P na2_1 with a = 21.166 (4) Å, b = 10.096 (3) Å, c = 19.397 (5) Å, Z = 4, R = 0.032, Rw= 0.031 for 2703 observed reflections. From methanol, yellow crystals of [Cu_2(Lms)(NP)_2] MeOH were obtained in the monoclinic space group P 2_1/c with a = 10.531 (2) Å, b = 22.049 (6) Å, c = 18.27 (4) Å, β = 98.02 (2) °, Z = 4, R = 0.052, Rw = 0.051 for 4328 observed reflections. The two structures are similar except that the yellow form exhibits a coordinated three-centered bond absent from the orange form.