Brym Markus, Forsyth Craig M, Jones Cameron, Junk Peter C, Rose Richard P, Stasch Andreas, Turner David R
School of Chemistry, Monash University, Clayton, 3800, Australia.
Dalton Trans. 2007 Aug 14(30):3282-8. doi: 10.1039/b705202b. Epub 2007 Jun 14.
Metathesis reactions of the alkali metal formamidinates M(RNC(H)NR), M = Li or K; R = C(6)H(3)-2,6-Pr(i)(2) (L(1)), C(6)H(3)-2,6-Et(2) (L(2)); C(6)H(2)-2,4,6-Me(3) (L(3)), C(6)H(3)-2,6-Me(2) (L(4)) or C(6)H(4)-2-Ph (L(5)), with BiX(3) (X = Cl or Br) gave a range of bismuth(iii) formamidinate complexes Bi(L)Br(micro-Br)(thf) (L = L(1), L(4)), [{Bi(L(1))Cl(2)(thf)}(2)Bi(L(1))Cl(2)], [Bi(L)(2)X] (L = L(2), L(5), X = Br; L = L(1), X = Cl), and [Bi(L)(3)] (L = L(2), L(3)). An analogous organometallic complex Bi(L(1))(2)Bu(n) was also isolated as a side product in one instance. Structural characterisation of the di-halide complexes show symmetrical dimers for X = Br, with two bromide bridges, and a coordinated thf molecule on each Bi atom, whereas for X = Cl a thf deficient species was crystallised, and has a weakly associated trinuclear array with two coordinated thf molecules per three Bi atoms. Complexes of the form Bi(L)(2)X (X = Br, Cl, Bu(n)) and Bi(L)(3) all have monomeric structures but the Bi(L)(3) species show marked asymmetry of the formamidinate binding, suggesting that they have reached coordination saturation.
碱金属甲脒盐M(RNC(H)NR)（M = Li或K；R = C(6)H(3)-2,6-Pr(i)(2) （L(1)）、C(6)H(3)-2,6-Et(2) （L(2)）；C(6)H(2)-2,4,6-Me(3) （L(3)）、C(6)H(3)-2,6-Me(2) （L(4)）或C(6)H(4)-2-Ph （L(5)））与BiX(3)（X = Cl或Br）的复分解反应生成了一系列铋(iii)甲脒配合物Bi(L)Br(μ-Br)(thf)（L = L(1)、L(4)）、[{Bi(L(1))Cl(2)(thf)}(2)Bi(L(1))Cl(2)]、[Bi(L)(2)X]（L = L(2)、L(5)，X = Br；L = L(1)，X = Cl）以及[Bi(L)(3)]（L = L(2)、L(3)）。在一个实例中还分离出了一种类似的有机金属配合物Bi(L(1))(2)Bu(n)作为副产物。二卤化物配合物的结构表征表明，对于X = Br，其为对称二聚体，有两个溴桥，每个Bi原子上有一个配位的thf分子；而对于X = Cl，结晶出的是thf不足的物种，并且具有一个弱关联的三核阵列，每三个Bi原子有两个配位的thf分子。Bi(L)(2)X（X = Br、Cl、Bu(n)）和Bi(L)(3)形式的配合物均具有单体结构，但Bi(L)(3)物种显示出甲脒结合的明显不对称性，表明它们已达到配位饱和。
