RHODAOXETANE - SYNTHESIS, STRUCTURE, AND THEORETICAL EVALUATION

被引:40
作者
CALHORDA, MJ
GALVAO, AM
UNALEROGLU, C
ZLOTA, AA
FROLOW, F
MILSTEIN, D
机构
[1] Univ Tecn Lisboa, INST SUPER TECN, P-1096 LISBON, PORTUGAL
[2] CTR QUIM ESTRUT, IST, P-1096 LISBON, PORTUGAL
[3] WEIZMANN INST SCI, DEPT ORGAN CHEM, IL-76100 REHOVOT, ISRAEL
关键词
D O I
10.1021/om00032a062
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Oxidative addition of Rh(PMe3)3Cl to HOCMe2CH2Br leads to the beta-hydroxy complex 4. Deprotonation of 4 with (Me3Si) 2 NK leads to the rhodaoxetane 5. 4 and 5 were crystallographically characterized, allowing direct evaluation of the structural consequences of ring closure. The oxetane ring in 5 is planar and it exhibits Rh-C [2.069(10) angstrom] and C-0 [1.416(12) angstrom], significantly shorter than the equivalent bonds in 4. The planarity of the oxetane ring was assigned to a minimization of repulsive interactions between filled orbitals of the metal and oxygen in this geometry, a result of a theoretical study based on extended Huckel calculations. 4 also shows a substantial Cl...H hydrogen bond. 5 can also be obtained by direct oxidative addition of Rh(PMe3)3Br to isobutyleneoxide, providing the first direct demonstration of oxidative addition of a metal complex to a simple epoxide to yield a metallaoxetane. Calculations were done in order to probe the reactivity of the metallacycle.
引用
收藏
页码:3316 / 3325
页数:10
相关论文
共 69 条
[41]   SYNTHESIS AND CRYSTAL-STRUCTURE OF 3,3,4-TRICYANO-2,2-BIS(TRIPHENYLPHOSPHINE)-1-OXA-2-PLATINACYCLOBUTANE [J].
LENARDA, M ;
PAHOR, NB ;
CALLIGARIS, M ;
GRAZIANI, M ;
RANDACCIO, L .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1978, (04) :279-282
[42]  
March J., 1985, ADV ORG CHEM, P88
[43]   MO THEORY MADE VISIBLE [J].
MEALLI, C ;
PROSERPIO, DM .
JOURNAL OF CHEMICAL EDUCATION, 1990, 67 (05) :399-402
[45]   SELECTIVE TRANSFORMATION OF VICINAL-DISUBSTITUTED EPOXIDES INTO KETONES BY HOMOGENEOUS RHODIUM CATALYSTS [J].
MILSTEIN, D ;
BUCHMAN, O ;
BLUM, J .
JOURNAL OF ORGANIC CHEMISTRY, 1977, 42 (13) :2299-2308
[46]  
MILSTEIN D, 1982, J AM CHEM SOC, V104, P3733
[47]   NOVEL OXIRANE FORMATION VIA 1-METALLA-2-OXACYCLOBUTANES [J].
MIYASHITA, A ;
ISHIDA, J ;
NOHIRA, H .
TETRAHEDRON LETTERS, 1986, 27 (19) :2127-2130
[48]   THE REACTIONS OF PLATINUM(0) AND PALLADIUM(0) TERTIARY PHOSPHINE COMPLEXES WITH PHENYL DICYANOOXIRANES [J].
OSBORNE, RB ;
IBERS, JA .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1982, 232 (04) :371-385
[49]   REACTIONS OF SOME OXIRANES WITH RHODIUM(I) AND IRIDIUM(I) SPECIES [J].
OSBORNE, RB ;
IBERS, JA .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1982, 232 (03) :273-277
[50]   TITANIUM-MEDIATED METHYLENE-TRANSFER REACTIONS - DIRECT CONVERSION OF ESTERS INTO VINYL ETHERS [J].
PINE, SH ;
ZAHLER, R ;
EVANS, DA ;
GRUBBS, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (09) :3270-3272