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Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates
Published on: February 15, 2016
Studies on the Synthetic System of V/Ag/S Cluster Compounds and Structural Characterizations of V(2)AgS(4),
Hongping Zhu1, Qiutian Liu, Xiaoying Huang
1State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.
Abstract:
The reaction system (NH(4))(3)VS(4)/Ag(PPh(3))(2)Cl/R(2)dtcNa in CH(3)CN was studied to afford two V(2)Ag(1)(-)(2)S(4) cubanelike cluster compounds and a trinuclear V(3)O(3)S(2) complex. (Et(4)N)[V(2)AgS(4)(Me(2)dtc)(2)(PPh(3))].(1)/(2)CH(3)CN ([Et(4)N]1.(1)/(2)CH(3)CN) crystallizes in the monoclinic space group P2(1)/c with a = 10.525(3) Å, b = 16.340(8) Å, c = 26.834(8) Å, beta = 101.28(2) degrees, and Z = 4. Complex (Et(4)N)(2)[V(2)Ag(2)S(4)(CS(3))(2)(PPh(3))(2)] ([Et(4)N](2)2) crystallizes in the monoclinic space group C2/c with a = 21.212(5) Å, b = 20.100(4) Å, c = 15.039(2) Å, beta = 102.72(2) degrees, and Z = 4. A stepwise aggregate process including a dinuclear V(2)Y(2)(&mgr;-S)(2) (Y = S, O) intermediate was suggested to explain the formation of 1, 2, and trinuclear anion [V(3)O(&mgr;-O)(2)(&mgr;-S)(2)(Et(2)dtc)(3)](-). Structural features of these complexes show that the V(2)Y(2)(&mgr;-S)(2) moiety can be seen as an independent unit to combine with other metal ion(s). A complex containing the [V(2)O(2)(&mgr;-S)(2)(Et(2)dtc)(2)](2)(-) (3) cluster anion was separated from a reaction system of (NH(4))(3)VS(4)/PPh(3)/Et(2)dtcNa, and its solvate complex {(Et(4)N)(3)Na[V(2)O(2)(&mgr;-S)(2)(Et(2)dtc)(2)](2)}(2).(1)/(2)CH(3)OH.H(2)O crystallizes in orthorhombic space group Pnn2 with a = 31.599(1) Å, b = 17.228(5) Å, c = 14.104(7) Å, and Z = 2. Infrared frequencies at 844-970 cm(-1) were associated with a V=O stretching vibration. The V=O additional coordination to the other metal ion gives rise to the red shift of the frequency. Proton and (51)V NMR spectra exhibit a paramagnetic V(IV) center existing in the trinuclear complex (Et(4)N)[V(3)O(&mgr;-O)(2)(&mgr;-S)(2)(Et(2)dtc)(3)] ([Et(4)N]4) and d(1)-d(1) coupling of V-V of the V(2)Y(2)(&mgr;-S)(2) moiety for these complexes. Two sets of the (31)P signals for 2at 16.6-19.3 ppm with equal intensity are attributed to (31)P-(107)Ag coupling and may well hide two V atoms in a similar environment. Cyclic voltammetries show some similar electrochemical behaviors between 3 and 4 indicated by a common couple at -0.7 V/-0.65 V and an oxidation peak at +0.7 to +0.6 V which are proposed to be due to redox in the V(2)O(2)(&mgr;-S)(2) moiety.
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