Adolf Ariane, Gonsior Marcin, Krossing Ingo
Universität Karlsruhe, Institut für Anorganische Chemie, Engesserstrasse Geb. 30.45, D-76128 Karlsruhe, Germany.
J Am Chem Soc. 2002 Jun 19;124(24):7111-6. doi: 10.1021/ja012760v.
Upon reacting P(4)S(3) with AgAl(hfip)(4) and AgAl(pftb)(4) [hfip = OC(H)(CF(3))(2); pftb = OC(CF(3))(3)], the compounds Ag(P(4)S(3))Al(hfip)(4) 1 and Ag(P(4)S(3))(2)(+)Al(pftb)(4) 2 formed in CS(2) (1) or CS(2)/CH(2)Cl(2) (2) solution. Compounds 1 and 2 were characterized by single-crystal X-ray structure determinations, Raman and solution NMR spectroscopy, and elemental analyses. One-dimensional chains of Ag(P(4)S(3))(x) (x = 1, 1; x = 2, 2) formed in the solid state with P(4)S(3) ligands that bridge through a 1,3-P,S, a 2,4-P,S, or a 3,4-P,P eta(1) coordination to the silver ions. Compound 2 with the least basic anion contains the first homoleptic metal(P(4)S(3)) complex. Compounds 1 and 2 also include the long sought sulfur coordination of P(4)S(3). Raman spectra of 1 and 2 were assigned on the basis of DFT calculations of related species. The influence of the silver coordination on the geometry of the P(4)S(3) cage is discussed, additionally aided by DFT calculations. Consequences for the frequently observed degradation of the cage are suggested. An experimental silver ion affinity scale based on the solid-state structures of several weak Lewis acid base adducts of type (L)AgAl(hfip)(4) is given. The affinity of the ligand L to the silver ion increases according to P(4) < CH(2)Cl(2) < P(4)S(3) < S(8) < 1,2-C(2)H(4)Cl(2) < toluene.
将P(4)S(3)与AgAl(hfip)(4)和AgAl(pftb)(4) [hfip = OC(H)(CF(3))(2); pftb = OC(CF(3))(3)]反应时，化合物Ag(P(4)S(3))Al(hfip)(4) 1和Ag(P(4)S(3))(2)(+)Al(pftb)(4) 2在CS(2)（1）或CS(2)/CH(2)Cl(2)（2）溶液中形成。化合物1和2通过单晶X射线结构测定、拉曼光谱和溶液核磁共振光谱以及元素分析进行了表征。固态下形成了Ag(P(4)S(3))(x)（x = 1, 1；x = 2, 2）的一维链，其中P(4)S(3)配体通过1,3 - P,S、2,4 - P,S或3,4 - P,P η(1)配位与银离子桥连。具有最弱碱性阴离子的化合物2包含首个均配金属(P(4)S(3))配合物。化合物1和2还包括长期以来所寻求的P(4)S(3)的硫配位。基于相关物种的密度泛函理论计算对1和2的拉曼光谱进行了归属。此外，借助密度泛函理论计算讨论了银配位对P(4)S(3)笼几何形状的影响。提出了对笼常见降解的影响。给出了基于几种(L)AgAl(hfip)(4)型弱路易斯酸碱加合物固态结构的实验性银离子亲和度标度。配体L对银离子的亲和力按P(4) < CH(2)Cl(2) < P(4)S(3) < S(8) < 1,2 - C(2)H(4)Cl(2) < 甲苯的顺序增加。
