Bowmaker Graham A, Hanna John V, Pakawatchai Chaveng, Skelton Brian W, Thanyasirikul Yupa, White Allan H
Department of Chemistry, University of Auckland, Private Bag 92019, Auckland, New Zealand.
Inorg Chem. 2009 Jan 5;48(1):350-68. doi: 10.1021/ic801310r.
Several synthetic strategies using copper(I) starting materials or copper(II) compounds and an in situ sulfite reductant have been used to systematically explore the chemistry of copper(I) complexes with thiourea and substituted thiourea ligands. This has resulted in the discovery of several new complexes and methods for the bulk synthesis of some previously reported complexes that had been prepared adventitiously in small quantity. The new complexes are (tu = thiourea, dmtu = N,N'-dimethylthiourea, etu = ethylenethiourea): [I(4)Cu(4)(tu)(6)].H(2)O, Cu(4)(tu)(10).tu.3H(2)O, [BrCu(dmtu)(3)], ICu(dmtu)(3), BrCu(etu)(2), [ICu(etu)(2)], ICu(etu)(2). [I(4)Cu(4)(tu)(6)].H(2)O has an adamantanoid structure, with four terminal iodide ligands and six doubly bridging tu ligands. In contrast to this, Cu(4)(tu)(10).tu.3H(2)O contains a tetranuclear cluster in which four of the tu ligands are terminal and the other six are doubly bridging. [BrCu(dmtu)(3)] is a mononuclear complex with tetrahedral coordination of copper by one bromide and three dmtu ligands, whereas Cu(dmtu)(3)I(2) has a centrosymmetric dimeric cation with two uncoordinated iodides, four terminal dmtu and two doubly bridging dmtu ligands, [(dmtu)(2)Cu(mu-S-dmtu)(2)Cu(dmtu)(2)]I(2). A reversal of this monomer to dimer trend from bromide to iodide is seen for the etu counterparts: BrCu(etu)(2) is a centrosymmetric dimer with two doubly bridging etu ligands, [(etu)BrCu(mu-S-etu)(2)CuBr(etu)], whereas [ICu(etu)(2)] is a trigonal planar monomer, although the novel [I(3)Cu(3)(etu)(6)] is also defined. Infrared and Raman spectra of the synthesized complexes were recorded and the metal-ligand vibrational frequencies have been assigned in many cases. The results confirm previously observed correlations between the vibrational frequencies and the corresponding bond lengths for complexes of the unsubstituted tu ligand. A mechanochemical/infrared method was used to synthesize [I(3)Cu(3)(etu)(6)] from CuI and etu, and to demonstrate the polymorphic transition from [ICu(etu)(2)] to [I(3)Cu(3)(etu)(6)].
已经采用了几种使用铜（I）起始原料或铜（II）化合物以及原位亚硫酸盐还原剂的合成策略，来系统地探索铜（I）与硫脲及取代硫脲配体形成的配合物的化学性质。这导致发现了几种新的配合物，以及一些用于大量合成某些先前偶然少量制备的已报道配合物的方法。新的配合物有（tu = 硫脲，dmtu = N,N'-二甲基硫脲，etu = 乙撑硫脲）：[I₄Cu₄(tu)₆]·H₂O、Cu₄(tu)₁₀·tu·3H₂O、[BrCu(dmtu)₃]、[ICu(dmtu)₃]₂、[BrCu(etu)₂]₂、[ICu(etu)₂]、[ICu(etu)₂]₃。[I₄Cu₄(tu)₆]·H₂O具有金刚烷型结构，有四个末端碘配体和六个双桥连tu配体。与此不同的是，Cu₄(tu)₁₀·tu·3H₂O包含一个四核簇，其中四个tu配体是末端的，另外六个是双桥连的。[BrCu(dmtu)₃]是一个单核配合物，铜通过一个溴和三个dmtu配体呈四面体配位，而[Cu(dmtu)₃]₂I₂有一个中心对称的二聚阳离子，带有两个未配位的碘、四个末端dmtu和两个双桥连dmtu配体，即[(dmtu)₂Cu(μ-S-dmtu)₂Cu(dmtu)₂]I₂。对于etu类似物，从溴化物到碘化物观察到这种单体到二聚体趋势的反转：[BrCu(etu)₂]₂是一个中心对称的二聚体，带有两个双桥连etu配体，即[(etu)BrCu(μ-S-etu)₂CuBr(etu)]，而[ICu(etu)₂]是一个三角平面单体，不过也确定了新型的[I₃Cu₃(etu)₆]。记录了合成配合物的红外和拉曼光谱，并且在许多情况下对金属 - 配体振动频率进行了归属。结果证实了先前观察到的未取代tu配体配合物的振动频率与相应键长之间的相关性。采用机械化学/红外方法从CuI和etu合成了[I₃Cu₃(etu)₆]，并证明了从[ICu(etu)₂]到[I₃Cu₃(etu)₆]的多晶型转变。
