Structural and coordination properties of 1,2-bis(cyclopropyl)-3,4-bis(2,4,6-tri-tert-butylphenyl)-3,4-diphosphinidenecyclobutene prepared by dehydrogenative homocoupling of 3-cyclopropyl-l-(2,4,6-tri-tert-butylphenyl)-1-phosphaallene

被引:0
作者
Ito, S [1 ]
Freytag, M [1 ]
Yoshifuji, M [1 ]
机构
[1] Tohoku Univ, Grad Sch Sci, Dept Chem, Aoba Ku, Sendai, Miyagi 9808578, Japan
关键词
D O I
暂无
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
According to a protocol for the synthesis of phosphaallenes we recently established, 3-cyclopropyl-1-(2,4,6-tri-tert-butylphenyl)-1-phosphallene was obtained from (Z)-2-bromo-3-cyclopropyl-1-(2,4,6tri-tert-butylphenyl)-1-phosphapropene. A novel bidentate ligand, 1,2-bis(cyclopropyl)-3,4-bis(2,4,6tri-tert-butylphenyl)-3,4-diphosphinidenecyclobutene, was prepared by oxidative homocoupling of 3-cyclopropyl-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaallene in the presence of butyllithium, together with the generation of hydrogen gas. The 1,2-bis(cyclopropyl)-3,4-diphosphinidenecyclobutene was allowed to react with (tht)AuCl (tht = tetrahydrothiophene) to afford the corresponding digold(I) complex of a six-membered metallacycle containing the P=C-C=P skeleton. The molecular structures of the 2-bromo-3-cyclopropyl-1-phosphapropene, 1,2-bis(cyclopropyl)-3,4-diphosphinidenecyclobutene and the digold complex were unambiguously determined by X-ray crystallography and are discussed from the point of view of the cyclopropyl conjugation.
引用
收藏
页码:710 / 713
页数:4
相关论文
共 34 条
[1]   SIR92 - a program for automatic solution of crystal structures by direct methods [J].
ALTOMARE, A ;
CASCARANO, G ;
GIACOVAZZO, G ;
GUAGLIARDI, A ;
BURLA, MC ;
POLIDORI, G ;
CAMALLI, M .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1994, 27 :435-435
[2]   LOW COORDINATED PHOSPHORUS-COMPOUNDS .56. VALENCE ISOMERIZATION OF A 3,4-DIPHOSPHA-1,5-HEXADIYNE WITH FORMATION OF A 3,4-BIS(PHOSPHAMETHYLENE)-1-CYCLOBUTENE [J].
APPEL, R ;
WINKHAUS, V ;
KNOCH, F .
CHEMISCHE BERICHTE-RECUEIL, 1987, 120 (02) :243-245
[3]   STRUCTURE OF HEXACYCLOPROPYLBENZENE [J].
BAR, I ;
BERNSTEIN, J ;
CHRISTENSEN, A .
TETRAHEDRON, 1977, 33 (23) :3177-3180
[4]  
BEURSKENS PT, 1994, DIRDIF94 PROGRAM SYS
[5]  
Dillon K. B., 1998, PHOSPHORUS CARBON CO
[6]  
Haumann T, 1997, LIEBIGS ANN-RECL, P2047
[7]   An efficient synthetic method of 1-(2,4,6-tri-t-butylphenyl)-3-phenyl-1-phosphaallenes [Mes*P=C=CR-Ph; R = H, SiMe3] from dibromophosphaethene [Mes*P=CBr2] (Mes*=2,4,6-t-Bu3C6H2) [J].
Ito, S ;
Sekiguchi, S ;
Freytag, M ;
Yoshifuji, M .
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 2005, 78 (06) :1142-1144
[8]   Formation and electrochemical properties of a 1,4-diphosphafulvene including formal dimerization of phosphaallene [J].
Ito, S ;
Sekiguchi, S ;
Yoshifuji, M .
JOURNAL OF ORGANIC CHEMISTRY, 2004, 69 (12) :4181-4184
[9]   Topochemical [2+2] dimerization of kinetically stabilized 1-phosphaallenes in the solid state [J].
Ito, S ;
Sekiguchi, S ;
Yoshifuji, M .
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2003, 2003 (24) :4838-4841
[10]  
ITO S, 2004, SCI REP TOHOKU U 1, V81, P17