ACYLIDENEPHOSPHINES AND ALKYLIDENEPHOSPHINES .33. LITHOXY-METHYLIDENEPHOSPHINE . DME AND LITHOXY-METHYLIDYNEPHOSPHINE . 2DME - SYNTHESES AND STRUCTURES
ACYLIDENEPHOSPHINES AND ALKYLIDENEPHOSPHINES .33. LITHOXY-METHYLIDENEPHOSPHINE . DME AND LITHOXY-METHYLIDYNEPHOSPHINE . 2DME - SYNTHESES AND STRUCTURES
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DOI：
10.1002/zaac.19926120113
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发表时间：
1992-06-01
影响因子：
1.4
通讯作者：
WESTERHAUSEN, M
中科院分区：
文献类型：
--
作者：
BECKER, G;SCHWARZ, W;WESTERHAUSEN, M
二氢磷化锂。DME1)和甲酸乙酯以2：1的摩尔比在1，2-二甲氧基乙烷中反应，得到液态甲酰磷化锂。二甲醚的收率为87%。由于螯合配体DME络合的锂与羰基上的氧原子结合，因此该化合物必须被认为是亚甲基膦甲氧基甲酯。二甲醚(1)。根据晶体衍生物[5，61]的X-射线结构分析，这类分子发生二聚化，形成四元Li-O-Li-O环。核磁共振特征数据表明存在E-和Z-异构体(Delta-H-1-P：3.87和4.49；1J(HP)：150.8和136.5；Delta H-1-C：11.4和10.05；2J(HP)：6.1和81.2；3J(HH)：6.6和13.9；Delta-P-31：38.6和8.8；Delta-C-13=P：225.0和215.4 ppm；1J(C=P)：41.2和65.0cps)；在1，2-二甲氧基乙烷中，E：Z比为1.86：1。在双(三甲基硅基)磷化锂的类似反应中。1.6 THF1)和过量的碳酸二甲酯甲氧基甲基乙基膦。2二甲醚(2)是通过一种迄今鲜为人知的机制形成的。该化合物也可由二氢磷化锂-二甲醚合成，其晶型为单斜晶系P2(1)/n{a=880.6(2)；b=1296.6(2)；c=1 267.4(2)pm；β=96.07(2)℃；Z=41。X-射线结构分析(R(W)=0.052)得出P-C距离为155.5 pm，这对于三键来说是典型的。然而，119.8 pm的C-0键长度与单个键的标准值(139 Pm)相比是非常短的。碳和氧的178.50度和170.7度角对应于分子主链P=C-0-Li的预期线性构型。核磁共振特征数据如下：Delta-P-31-384.2，Delta-C-13 166.6 ppm，1j(c=p)41.5cps。
Lithium dihydrogenphosphide . DME1) and ethyl formate in a molar ratio of 2 : 1 react in 1,2-dimethoxyethane to give liquid lithium formylphosphide . DME in 87% yield. Since lithium complexed by the chelate ligand DME is bound to the oxygen atom of the carbonyl group, the compound has to be considered as lithoxy-methylidenephosphine . DME (1). According to x-ray structure analyses of crystalline derivatives [5, 61, molecules of this type dimerize forming a four membered Li-O-Li-O ring. Characteristic nmr-data show the presence of an E- and Z-isomer (delta-H-1-P: 3.87 and 4.49; 1J(HP): 150.8 and 136.5; delta H-1-C: 11.4 and 10.05; 2J(HP): 6.1 and 81.2 ; 3J(HH): 6.6 and 13.9; delta-P-31: 38.6 and 8.8; delta-C-13 = P: 225.0 and 215.4 ppm; 1J(C=P): 41.2 and 65.0 cps); in 1,2-dimethoxyethane an E : Z ratio of 1.86: 1 is found.In a similar reaction of lithium bis(trimethylsilyl)phosphide . 1.6 THF1) with excess dimethyl carbonate lithoxy-methylidynephosphine . 2 DME (2) is formed via an up to now poorly understood mechanism. The compound can also be prepared from lithium dihydrogenphosphide - DME; it crystallizes in the monoclinic space group P2(1)/n {a = 880.6(2); b = 1296.6(2); c = 1 267.4(2) pm; beta = 96.07(2)-degrees at -100 +/- 3-degrees-C; Z = 41. An x-ray structure analysis (R(w) = 0.052) gives a P-C distance of 155.5 pm which is typical for a triple bond. The C-0 bond length of 119.8 pm, however, is extremely short compared to the standard value of a single bond (139 pm). Angles of 178.50 and 170.7-degrees at the carbon and oxygen correspond with the expected linear configuration of the P=C-0-Li backbone of the molecule. Characteristic nmr-data are as follow: delta-P-31 -384.2; delta-C-13 166.6 ppm; 1J(c=p) 41.5 cps.