Isolation of some sterically protected unsymmetrical diphosphenes: nature of the phosphorus-phosphorus double bond
Isolation of some sterically protected unsymmetrical diphosphenes: nature of the phosphorus-phosphorus double bond
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一些空间保护的不对称二磷菲的分离：磷-磷双键的性质
DOI：
10.1002/chin.198332257
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发表时间：
1983
期刊：
影响因子：
--
通讯作者：
K. Nishimoto
中科院分区：
文献类型：
--
作者：
M. Yoshifuji;Katsuhiro Shibayama;N. Inamoto;T. Matsushita;K. Nishimoto
实验部分。如前所述制备cij-（OC）4 M（NBD）（M= Cr，6 Mo，6 W7）、（OC）4 Mo（tmpa）、8和19。给出的红外谱带是CH_2Cl_2中的A_2、A_1和B、B_2 CO伸缩。2（首先由Allison等人2以4%产率制备）通过在室温下在2小时内将0.53 g（2.1 mmol）顺式-（OC）4Cr（NBD）在25 mL甲基环己烷中的溶液加入到0.69 g（4.6 mmol）1在25 mL甲基环己烷中的搅拌溶液中以49%产率合成。溶液继续搅拌4小时后，过滤沉淀的白色固体，用丙酮在弗罗里硅土柱上层析，得到0.48 g（49%）2。IR和~（31）P NMR参数与文献报道一致。类似地制备并通过将其溶解在CHCl 3中并用戊烷沉淀来纯化（产率36%; IR 2042，1955，1929 cm-1）。4及其配体异构体cv ′ s-（OC）4 Mo [P（CH 2 O）3 P][P（OCH 2）3 P]通过使用ds-（OC）4 Mo（tmpa）类似地制备，并在Florisil柱上用3：1己烷：乙酸乙酯进行色谱分离（异构体产率6.6%; IR 2039，1955，1936 cm-1;产率4.31%; IR 2041，1954，1938 cm-1）。通过将0.14g（0.30mmol）2和0.08g（0.30mmol）ris-（OC）4Cr（NBD）在35 mL CH 2Cl 2中的溶液溶解1天来制备。过滤后，除去溶剂，得到浅黄色固体，将其与3类似地纯化（产率85%; IR 2036，1960，1937 cm-1）。类似地制备6和7，不同之处在于将ds-（OC）4 Mo（tmpa）用于7产率6.86%，IR 2041，1963，1933 cm-1，产率7.86%; IR 2050，2036（均为A，2），1970，（5）如果将方案II中的中间体D进一步纯化，可以发生相对无应变的环闭合，形成含有8个金属原子的60元环大环。以5-9实现的高产率合成这种扩大的大环是出乎意料的。此外，这种大环的模型表明，它在不同的化学环境中具有一半的金属原子，在构象上是刚性的，因此产生了比5-9观察到的更复杂的NMR和IR光谱。(6)金河B。在“有机合成”中; J. J.，金河B.，编辑;学术出版社：纽约，1965年;第一卷。(7)King，RB; Fronzaglia，A. Inorg.Chem.1966，5，1837. (8)多布森，G.的R.; Faber，GC Inorg. Chim. Acta 1970，4，87. (9)Rathke，J. W.; Guyer，J. W.; Verkade，J. G. J. Org. Chem. 1970，35，2311。
Experimental Section. cij-(OC) 4M (NBD)(M= Cr, 6 Mo, 6 W7),(OC) 4Mo (tmpa), 8 and l9 were made as described previously. Infrared bands given are for the A2, A}, and B, B2 CO stretches in CH2C12. 2 (first prepared in 4% yield by Allison et al. 2) was synthesized in 49% yield by adding a solution of 0.53 g (2.1 mmol) of cw-(OC) 4Cr (NBD) in 25 mL of methylcyclohexane to a stirred solution of 0.69 g (4.6 mmol) of 1 in 25 mL of methylcyclohexane at room temperature over a period of 2 h. After the solution continued stirring for 4 h, the white solid that precipitated was filtered and chromatographed with acetone on a Florisil column to yield 0.48 g (49%) of 2. The IR and and 31P NMR parameters agree with those reported earlier. 2 3 was similarly prepared and purified by dissolving it in CHC13 and precipitating with pentane (yield 36%; IR 2042, 1955, 1929 cm" 1). 4 and its ligand isomer cv's-(OC) 4Mo [P (CH20) 3P][P (OCH2) 3P] were prepared analogously by using ds-(OC) 4Mo (tmpa) and chromatographed on a Florisil column with 3: 1 hexane: ethyl acetate (yield of isomer 6.6%; IR 2039, 1955, 1936 cm" 1; yield of 4 31%; IR 2041, 1954, 1938 cm" 1).5 was made by refluxing a solution of 0.14 g (0.30 mmol) of 2 and 0.08 g (0.30 mmol) of ris-(OC) 4Cr (NBD) in 35 mL of CH2C12 for 1 day. After filtration, solvent removal left a light yellow solid, which was purified similarly to3 (yield 85%; IR 2036, 1960, 1937 cm" 1). 6 and 7 were prepared analogously except that ds-(OC) 4Mo (tmpa) was used for 7 (yield of 6 86%; IR 2041, 1963, 1933 cm" 1; yield of 7 86%; IR 2050, 2036 (both A, 2), 1970,(5) If intermediate D in Scheme II were to polymerize further, relatively strainless ring closure could occur to form a 60-membered ring macrocycle containing 8 metal atoms. Synthesis of such an enlarged macrocycle in the high yields realized for 5-9 is unexpected. Moreover, a model of such a macrocycle reveals that it would be conformationally rigid with half the metal atoms in a different chemical environment, thusengendering substantially more complicated NMR and IR spectra than are observed for 5-9.(6) King, R. B. In “Organometallic Synthesis”; Eisch, J. J., King, R. B., Eds.; Academic Press: New York, 1965; Vol. I.(7) King, RB; Fronzaglia, A. Inorg. Chem. 1966, 5, 1837.(8) Dobson, G. R.; Faber, GC Inorg. Chim. Acta 1970, 4, 87.(9) Rathke, J. W.; Guyer, J. W.; Verkade, J. G. J. Org. Chem. 1970, 35, 2311.