Studies on Sterically Protected Multiple Bonding Involving Low Coordinated Phosphorus Atoms

涉及低配位磷原子的空间保护多重键合研究

• 批准号: 02403008
• 负责人: YOSHIFUJI Masaaki
• 金额: $ 22.72万
• 依托单位: TOHOKU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (A)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02403008/
• 关键词: Low coordination; Steric protection; Organophosphorus compounds; Diphosphene; Diphosphaallene; Diphosphabutatriene; Phosphaalkyne; P-NMR; PーNMR

Sterically protected phosphorus containing unusual compounds in low coordination states were prepared by utilizing the 2,4,6-tri-t-butylphenyl moiety (here abbreviated to the Ar group) as a protective group. Such unusual organophosphorus compounds as diphosphene (-P=P-), 1,3-diphosphaallene (-P=C=P-), and phosphaalkyne (-C*P) having low coordinated phosphorus atom(s) of coordination number 2 or 1 were isolated and characterized as kinetically stable compounds.Protective groups other than the Ar group have been developed to utilize the stabilization of low coordinated organophosphorus compounds as follows. Attempts to prepare diphosphenes involving 2,6-di-t-butylphenyl, 2,4,6-tri-t-pentylphenyl, 1,2,3,4,5,6,7,8-octahydro-1,1,4,4,5,5,8,8-octamethyl-9-anthryl, and 2,4-di-t-butyl-6-dimethylaminophenyl were successful. Strong electron-withdrawing groups, such as 2,4,6-tris(trifluoromethyl)phenyl and 2,6-bis(trifluoromethyl)phenyl, were also useful as a protective auxiliary of diphosphenes as well as unsymmetrical diphosphenes.A preparative method of 1,3-diphosphaallenes has been developed involving addition reaction of dichlorocarbene to diphosphenes leading to dichlorodiphosphiranes, which were further converted to diphosphaallenes with an appropriate alkyllithium reagent. This preparative method has been successful in preparation of some unsymmetrical diphosphaallenes' starting from unsymmetrical diphosphenes. Attempted preparations of the extended phosphacumulenes such as phosphabutatriene (-P=C=C=C ) and diphosphabutatriene (-P=C=C=P-) have been successful by this method.A new preparative method of phosphaalkynes has been developed involving elimination and intramolecular rearrangement of 1-chloro-2-phosphaethenyllithiums and the ^<31>P NMR studies have been made in an attempt to observe intermediacy of phosphorus analogue of isonitrile during this unusual rearrangement reaction.

通过利用2，4，6-三叔丁基苯基部分（这里缩写为Ar基团）作为保护基，制备了低配位态的空间保护的含磷不寻常化合物。一些罕见的有机磷化合物如双磷烯（-P=P-）、1，3-双磷杂丙二烯（-P=C=P-）和磷杂炔（-C*P）具有配位数为2或1的低配位磷原子，被分离出来并表征为动力学稳定的化合物。尝试制备包括2，6-二叔丁基苯基、2，4，6-三叔戊基苯基、1，2，3，4，5，6，7，8-八氢-1，1，4，4，5，5，8，8-八甲基-9-蒽基和2，4-二叔丁基-6-二甲氨基苯基的二膦是成功的。强吸电子基团如2，4，6-三（三氟甲基）苯基和2，6-双（三氟甲基）苯基也可作为双膦和不对称双膦的保护助剂。该方法已成功地应用于不对称二磷杂环戊二烯类化合物的合成。利用该方法成功地制备了磷杂环戊二烯（-P=C=C=C）和二磷杂环戊二烯（-P=C=C=P-）等磷杂环戊二烯类化合物，发展了1-氯-2-磷杂乙烯基锂的消除和分子内重排制备磷炔的新方法，并通过~ <31>1HNMR研究了该重排反应中异腈磷类似物的中间体.

项目成果

M.Yoshifuji,K.Toyota,H.Yoshimura,K.Hirotsu,and A,Okamoto: "Reactions of Dichlorocarbene with Sterically Protected Phosphaallene and 1,3ーDiphosphaallene" J.Chem.Soc.Chem.Commun.124-125 (1991)

M. Yoshifuji、K. Toyota、H. Yoshimura、K. Hirotsu 和 A, Okamoto：“二氯碳烯与空间保护的磷烯和 1,3-二磷烯的反应”J.Chem.Soc.Chem.Commun.124-125（ 1991)

K. Toyota: "Preparation of Group-6Metal(0)Carbonyl Complexes of Chelate Type Containing Diphosphinidenecyclobutene as a Bidentate Ligand" Chem. Lett.1991. 2079

K. Toyota：“含有二磷亚膦环丁烯作为双齿配体的螯合型 6 族金属 (0) 羰基配合物的制备” Chem。

M.Yoshifuji: "Preparation and Attempted Photoreaction of Diphosphenes Bearing 2,4,6-Tris(trifluoromethyl)phenyl Group" Science Reports,Tohoku University,Ser.1.

M.Yoshifuji：“带有2,4,6-三(三氟甲基)苯基基团的二磷菲的制备和尝试光反应”科学报告，东北大学，Ser.1。

M. Yoshifuji: "Reactions of Dichlorocarbene with Sterically Protected Phosphaallene and 1,3-Diphosphaallene" J. Chem. Soc. Chem. Commun.1991. 124

M. Yoshifuji：“二氯碳烯与空间保护的磷杂烯和 1,3-二磷杂烯的反应”J. Chem。

K. Toyota: "Synthesis and X-Ray Structure Analysis of cis-2,4-Bis(2,4,6-tri-t-butylphenyl)-1,2,4-oxadiphosphetane 2,4-Disulfide" Heteroatom Chem.

K.丰田：“顺式2,4-双(2,4,6-三叔丁基苯基)-1,2,4-氧杂二膦烷2,4-二硫化物的合成和X射线结构分析”杂原子化学。