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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Reaction behaviour of copper(I) and copper(II) salts towards P(C6H4CH2NMe2-2)(3) - the solid-state structures of {[P(C6H4CH2NMe2-2)(3)]CuOClO3]ClO4, {[P(C6H4CH2NMe2-2)(3)]Cu)ClO4, [P(C6H4CH2NMe2-2)(3)]CuONO2 and IP(C6H4CH2NMe2-2)(2)(C6H4CH2NMe2H+NO3-
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Reaction behaviour of copper(I) and copper(II) salts towards P(C6H4CH2NMe2-2)(3) - the solid-state structures of {[P(C6H4CH2NMe2-2)(3)]CuOClO3]ClO4, {[P(C6H4CH2NMe2-2)(3)]Cu)ClO4, [P(C6H4CH2NMe2-2)(3)]CuONO2 and IP(C6H4CH2NMe2-2)(2)(C6H4CH2NMe2H+NO3-

机译：铜（I）和铜（II）盐对P（C6H4CH2NMe2-2）（3）的反应行为-{[P（C6H4CH2NMe2-2）（3）] CuOClO3] ClO4，{[P（ C6H4CH2NMe2-2）（3）] Cu）ClO4，[P（C6H4CH2NMe2-2）（3）] CuONO2和IP（C6H4CH2NMe2-2）（2）（C6H4CH2NMe2H + NO3-

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The reaction behaviour Of P(C6H4CH2NMe2-2)(3) (1) towards different copper(II) and copper(l) salts of the type CuX2 (2a: X = BF4, 2b: X = PF6, 2c: X = ClO4, 2d: X = NO3, 2e: X = Cl, 2f. X = Br, 13: X = O2CMe) and CuX (5a: X ClO4, 5b: X = NO3, 5c: X = Cl, 5d: X = Br) is discussed. Depending on X, the transition metal complexes [P(C6H4CH2NMe2-2)(3)Cu]X-2 (3a: X = BF4, 3b: X = PF6), {[P(C6H4CH2NMe2-2)(3)]CuX}X (4: X = ClO4, 11a: X = Cl, 11b: X = Br, 14: X = O2CMe), {[P(C6H4CH2NMe2-2)(3)]Cu}ClO4 (6), [P(C6H4CH2NMe2-2)(3)]CuX (7a: X = Cl, 7b: X = Br, 10: X = ONP2), [P(C6H4CH2NMe2-2)(2)(C6H4CH2-NMe2H+NO3--2)]CuONO2 (9) and [P(C6H4CH2NMe2-2)(3)]CuCl}-CuCl2 (12) are accessible. While in 3a, 3b and 6 the phosphane I preferentially acts as tetrapodale ligand, in all other species only the phosphorus atom and two of the three C6H4CH2NMe2 side-arms are datively-bound to the appropriate copper ion. In solution a dynamic behaviour of the latter species is observed. Due to the coordination ability of X in 3a, 3b and 6 non-coordinating anions X- are present. However, in 4 one of the two perchlorate ions forms a dative oxygen-copper bond and the second perchlorate ion acts as counter ion to {[P(C6H4CH2NMe2-2)(3)]CuOClO3}(+). In 7, 9 and 10 the fragments X (X = Cl, Br, ONO2) form a a-bond with the copper(l) ion. The acetate moiety in 14 acts as chelating ligand as it could be shown by IR-spectroscopic studies.All newly synthesised cationic and neutral copper(l) and copper(II) complexes are representing stable species.Redox processes are involved in the formation of 9 and 12 by reacting I with 2.The solid-state structures of 4, 6, 9 and 10 are reported. In the latter complexes the copper(II) (4) or copper(l) ion (6, 9, 10) possesses the coordination number 4. This is achieved by the formation of a phosphorus- and two nitrogen-copper- (4, 9, 10) or three (6) nitrogen-copper dative bonds and a coordinating (4) or a-binding (9, 10) ligand X. In 6 all three nitrogen and the phosphorus atoms are coordinatively bound to copper, while X acts as non-coordinating counter-ion. Based on this, the respective copper ion occupies a distorted tetrahedral coordination sphere. While in 4 and 10 a free, neutral Me2NCH2 side-arm is present, which rapidly exchanges in solution with the coordinatively-bound Me2NCH2 fragments, this unit is protonated in 10. NO3- acts as counter ion to the CH2NMe2H+ moiety. In all structural characterized complexes 6-membered boat-like CuPNC3 cycles are present.
机译：P（C6H4CH2NMe2-2）（3）（1）对CuX2类型的不同铜盐（II）和铜盐（1）的反应行为（2a：X = BF4，2b：X = PF6，2c：X = ClO4 ，2d：X = NO3，2e：X = Cl，2f.X = Br，13：X = O2CMe）和CuX（5a：X ClO4，5b：X = NO3，5c：X = Cl，5d：X = Br ）进行了讨论。取决于X，过渡金属络合物[P（C6H4CH2NMe2-2）（3）Cu] X-2（3a：X = BF4，3b：X = PF6），{[P（C6H4CH2NMe2-2）（3）] CuX } X（4：X = ClO4，11a：X = Cl，11b：X = Br，14：X = O2CMe），{[P（C6H4CH2NMe2-2）（3）] Cu} ClO4（6），[P（ C6H4CH2NMe2-2）（3）] CuX（7a：X = Cl，7b：X = Br，10：X = ONP2），[P（C6H4CH2NMe2-2）（2）（C6H4CH2-NMe2H + NO3--2）]可以使用CuONO2（9）和[P（C6H4CH2NMe2-2）（3）] CuCl} -CuCl2（12）。在3a，3b和6中，膦I优先充当四足配体，而在所有其他物种中，只有磷原子和三个C6H4CH2NMe2侧臂中的两个臂适当地键合在适当的铜离子上。在解决方案中，观察到后一种物质的动态行为。由于X在3a，3b和6个非配位阴离子X-中的配位能力。但是，在4中，两个高氯酸根离子中的一个形成了固定的氧-铜键，第二个高氯酸根离子充当了{[P（C6H4CH2NMe2-2）（3）] CuOC10O3（+）的抗衡离子。在7、9和10中，片段X（X = Cl，Br，ONO2）与铜离子形成a键。红外光谱研究表明14中的乙酸盐部分是螯合配体，所有新合成的阳离子和中性铜（l）和铜（II）配合物均代表稳定的物种，氧化还原过程参与了9的形成和12通过使I与2反应而得到。报道了4、6、9和10的固态结构。在后者的络合物​​中，铜（II）（4）或铜（l）离子（6、9、10）的配位数为4。这是通过形成磷和两个氮-铜（4， 9、10）或三（6）个氮-铜配位键和一个配位（4）或a结合（9，10）配体X。在6个中，三个氮和磷原子均与铜配位结合，而X起作用作为非配位抗衡离子基于此，各个铜离子占据了扭曲的四面体配位球。在4和10中，存在一个游离的中性Me2NCH2侧臂，该侧臂在溶液中与配位结合的Me2NCH2片段快速交换，该单元在10中被质子化。NO3-充当CH2NMe2H +部分的抗衡离子。在所有具有结构特征的复合物中，均存在6元舟状CuPNC3循环。

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