Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay, Mumbai 400 076, India.
Inorg Chem. 2009 Feb 16;48(4):1398-406. doi: 10.1021/ic801256h.
Acyclic bis(cyclodiphosphazane) (t)BuHN((t)BuNP)(2)OCH(2) (2) containing alkoxo and amido functionalities was synthesized by reacting cis-[(t)BuHN((t)BuNP)(2)Cl] (1) with ethylene glycol and upon further treatment with 4 equiv of elemental sulfur or selenium affords the corresponding tetrachalcogenides (t)BuHN((t)BuNPE)(2)OCH(2) (3, E = S; 4, E = Se) in quantitative yield. The reaction of 2 with 2 equiv of elemental sulfur results in the oxidation of only the amido-phosphorus atoms to form the di(sulfide) derivative (t)BuHN(S)P(mu-(t)BuN)POCH(2) (5). The reaction of 2 with 2 equiv of PdCl(eta(3)-C(3)H(5)) afforded the tetrametallic complex [{Pd(eta(3)-allyl)Cl}(4){(t)BuHN((t)BuNP)(2)OCH(2)}(2)] (7) containing four independent [PdCl(2)(eta(3)-C(3)H(5))] moieties each coordinated to a phosphorus atom. In contrast, the reaction between Pd(PEt(3))Cl(2) and 2 leads to the addition of two metal atoms with the formation of [{Pd(PEt(3))Cl}(2){(t)BuHN((t)BuNP)(2)OCH(2)}(2)] (8), in which alternating phosphorus atoms of the bis(cyclodiphosphazane) are coordinated to palladium. Interestingly, the palladium(II) atom coordinated to the phosphorus atom bearing the t-butylamino substituent adopts a trans geometry, whereas that coordinated to the phosphorus atom connected to the -OCH(2)CH(2)O- linker prefers a cis conformation. The reaction between 2 and Rh(COD)Cl produces exclusively the bimetallic complex [{Rh(COD)Cl}(2){(t)BuHN((t)BuNP)(2)OCH(2)}(2)] (6) irrespective of the stoichiometry of the reactants and the reaction conditions. In complex 6, only the alkoxo-phosphorus atoms are coordinated. However, complex 6 upon treatment with AuCl(SMe(2)) in a 1:2 ratio gives the heterometallic tetrasubstituted complex [{Rh(COD)Cl}(2)(AuCl)(2){(t)BuHN((t)BuNP)(2)OCH(2)}(2)] (10). The reaction between 4 equiv of AuCl(SMe(2)) and 2 resulted in the formation of a tetrametallic gold complex [(AuCl)(4){(t)BuHN((t)BuNP)(2)OCH(2)}(2)] (9). The crystal structures of 2-4 and 7-10 are reported.
含有烷氧基和酰胺基官能团的非循环双（环二磷杂环戊烷）(t)BuHN((t)BuNP)(2)OCH(2)（2）是通过将顺式-[(t)BuHN((t)BuNP)(2)Cl]（1）与乙二醇反应，并进一步与 4 当量的元素硫或硒反应合成的，得到相应的四卤化物(t)BuHN((t)BuNPE)(2)OCH(2)（3，E=S；4，E=Se），产率为定量的。2 与 2 当量的元素硫反应仅导致酰胺磷原子被氧化，形成二（硫代）衍生物(t)BuHN(S)P(mu-(t)BuN)POCH(2)（5）。2 与 2 当量的PdCl(eta(3)-C(3)H(5))反应得到含有四个独立的[PdCl(2)(eta(3)-C(3)H(5))]部分的四金属配合物[{Pd(eta(3)-allyl)Cl}(4){(t)BuHN((t)BuNP)(2)OCH(2)}(2)]（7），每个[PdCl(2)(eta(3)-C(3)H(5))]部分都与一个磷原子配位。相比之下，Pd(PEt(3))Cl(2)与 2 之间的反应导致两个金属原子的加成，形成[{Pd(PEt(3))Cl}(2){(t)BuHN((t)BuNP)(2)OCH(2)}(2)]（8），其中双（环二磷杂环戊烷）的交替磷原子与钯配位。有趣的是，与叔丁基氨基取代的磷原子配位的钯（II）原子采用反式几何构型，而与连接-OCH(2)CH(2)O-链接的磷原子配位的钯原子则倾向于顺式构象。2 与Rh(COD)Cl的反应无论反应物的化学计量比和反应条件如何，都只产生双金属配合物[{Rh(COD)Cl}(2){(t)BuHN((t)BuNP)(2)OCH(2)}(2)]（6）。在配合物 6 中，只有烷氧基磷原子被配位。然而，配合物 6 在与 AuCl(SMe(2))以 1:2 的比例处理时，得到了杂金属四取代配合物[{Rh(COD)Cl}(2)(AuCl)(2){(t)BuHN((t)BuNP)(2)OCH(2)}(2)]（10）。4 当量的 AuCl(SMe(2))与 2 的反应导致形成四金属金配合物[(AuCl)(4){(t)BuHN((t)BuNP)(2)OCH(2)}(2)]（9）。报道了 2-4 和 7-10 的晶体结构。
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