Formation of 1,3-Diphosphacyclobutadiene Complexes from Phosphaalkynes and Their Coordination Behavior: 1,3-Diphosphacyclobutadiene Complexes
Formation of 1,3-Diphosphacyclobutadiene Complexes from Phosphaalkynes and Their Coordination Behavior: 1,3-Diphosphacyclobutadiene Complexes
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由磷炔形成 1,3-二磷杂环丁二烯配合物及其配位行为：1,3-二磷杂环丁二烯配合物
DOI：
10.1002/ejic.201301299
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发表时间：
2014
影响因子：
2.3
通讯作者：
M. Scheer
中科院分区：
文献类型：
--
作者：
E.-M. Rummel;M. Eckhardt;M. Bodensteiner;E. V. Peresypkina;M. Scheer
用[(Cp″‘ Co)2tol] （Cp″’ = η5‐C5H2tBu3, tol =甲苯）合成了一种新的1,3‐二磷酸配合物[Cp″‘ Co(η4‐P2C2tBu2)] （1a）和[Cp″’ Co(η4‐P2C2iPr2)] (1b)，并研究了它们与Lewis酸W(Co) 4和CuIhalides的反应。b1b与W(CO)4(nbd) （nbd =降冰片二烯）反应生成配合物[(Cp″' CO) (μ,η4:1‐{PCiPr}2)]2W(CO)4(2)与两个二磷酸配合物b1b配位转移到中心W(CO)4部分。根据化学计量的不同，a与卤化物的反应会产生不同的产物。二聚体3a - c[(Cp″′Co)(μ,η4:1‐{PCtBu}2)Cu(μ - X)]2（3a: X = Cl;3b: X = Br,3c: X = I）在1:1的比例下分离得到，而过量的CuX则得到二维聚合物[({Cp″′Co}{μ3,η4:1:1‐（PCtBu）2})2(Cu{μ3‐X})4]n（6a: X = Cl,6b: X = Br,6c: X = I）。由1a1b与cur和CuI以1:2或2:3的比例反应得到一维聚合物[({Cp″‘ Co}{μ3,η4:1:1‐（PCR）2})({Cp″’ Co}{μ3,η4:1‐（PCR）2})(Cu{μ3‐X})4]n（4a: X = Br, R =iPr,4b: X = I, R =iPr,4c: X = I, R =tBu）。从a与CuI的反应中，用CH3CN进行结晶分离得到了第二产物[({Cp″' Co}{μ3,η4:1:1‐（PCtBu）2})(Cu{μ3‐I})4(MeCN)2]n(5)]。采用光谱学、X射线晶体学和31p魔角旋转（MAS） NMR对产物进行了全面表征。
By using [(Cp″′Co)2tol] (Cp″′ = η5‐C5H2tBu3, tol = toluene), a new synthesis of the 1,3‐diphosphete complexes [Cp″′Co(η4‐P2C2tBu2)] (1a) and [Cp″′Co(η4‐P2C2iPr2)] (1b) was found, and their reactions with the Lewis acids W(CO)4and CuIhalides were investigated. The reaction of1bwith W(CO)4(nbd) (nbd = norbornadiene) leads to the complex [(Cp″′Co)(μ,η4:1‐{PCiPr}2)]2W(CO)4(2) with the two diphosphete complexes1bcoordinatedtransto a central W(CO)4moiety. The reactions of1awith CuIhalides result in different products depending on the stoichiometry. In a 1:1 ratio, the dimeric compounds3a–c[(Cp″′Co)(μ,η4:1‐{PCtBu}2)Cu(μ‐X)]2(3a: X = Cl;3b: X = Br,3c: X = I) were isolated, whereas an excess of CuX gave the two‐dimensional polymers [({Cp″′Co}{μ3,η4:1:1‐(PCtBu)2})2(Cu{μ3‐X})4]n(6a: X = Cl,6b: X = Br,6c: X = I). From the reaction of1aand1bwith CuBr and CuI in a 1:2 or 2:3 ratio, the one‐dimensional polymers [({Cp″′Co}{μ3,η4:1:1‐(PCR)2})({Cp″′Co}{μ,η4:1‐(PCR)2})(Cu{μ3‐X})4]n(4a: X = Br, R =iPr,4b: X = I, R =iPr,4c: X = I, R =tBu) are formed. From the reaction of1awith CuI, a second product, [({Cp″′Co}{μ3,η4:1:1‐(PCtBu)2})(Cu{μ3‐I})4(MeCN)2]n(5), was isolated by using CH3CN for crystallization. The products were comprehensively characterized by spectroscopic methods, X‐ray crystallography, and31P magic angle spinning (MAS) NMR spectroscopy.
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影响因子：
2.3
作者：
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影响因子：
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影响因子：
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影响因子：
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作者：
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DOI：
10.1002/cber.19971301022
发表时间：
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期刊：
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影响因子：
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作者：
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通讯作者：
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