Preparation and properties of molybdenum and tungsten dinitrogen complexes. 8. Diazoalkane complexes of molybdenum and tungsten
Preparation and properties of molybdenum and tungsten dinitrogen complexes. 8. Diazoalkane complexes of molybdenum and tungsten
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钼钨二氮配合物的制备及性能。
DOI：
10.1002/chin.197850279
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发表时间：
1978
期刊：
影响因子：
--
通讯作者：
Y. Uchida
中科院分区：
文献类型：
--
作者：
M. Hidai;Y. Mizobe;Maki Sato;T. Kodama;Y. Uchida
The hydrazido (2—) complexes [MF (NNH2)(dpe) 2][BF4](M= Mo or W, dpe= Ph2PCH2CH2PPh2) obtained from trans-[M (N2) 2 (dpe) 2] and HBF4 in THF readily condense with a variety of aldehydes and ketones to produce a new se-ries of diazoalkane or hydrazone-type complexes [MF (NN= CRR')(dpe) 2][BF4] in good yields. This reaction is remarkably accelerated in the presence of a trace of an acid. The structure of the diazoalkane complex [WFjN-N—CfCHa)-CFhCOCHsKdpeh][BF4]-THF has been determined from three-dimensional x-ray counter data. The complex crystallized in space group P\with a= 13.577 (15), b= 21.440 (25), c= 11.204 (13) Á; a= 102.36 (3), ß= 100.00 (3), y= 70.27 (5); V= 2980.5 (58) Á3; and Z= 2. The coordination geometry about the tungsten atom is octahedral with the diazoalkane ligand and fluoride anion in a trans position. The WNN linkage is essentially linear and the angle NNC is 125.2 (19). The WN, NN, and NC distances are 1.770 (17), 1.317 (25), and 1.300 (30) Á, respectively. The methyl group attached to the C= N bond is held in a distorted sandwich position relative to two phenyl groups, which accounts for the unusually higher shift of the methyl resonance in the NMR spectrum.The formation of carbon-nitrogen bonds from coordinat-ed dinitrogen is an important elementary step for the direct conversion of dinitrogen intoorganonitrogen compounds. The first examples of formation of organonitrogenligands from coordinated dinitrogen were found in the reaction of organic acid halides with [M (N2) 2 (dpe) 2](1)(=
