ACYCLIC CP(CO)2FE DISUBSTITUTED ETA-1-VINYLIDENE-ETA-2-ACETYLENE ISOMERIZATIONS

被引：40

作者：

BLY, RS

ZHONG, ZD

KANE, C

BLY, RK

机构：

[1] Department of Chemistry, University of South Carolina, Columbia

来源：

ORGANOMETALLICS | 1994年 / 13卷 / 03期

关键词：

D O I：

10.1021/om00015a024

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Acyclic, disubstituted vinylidene complexes, [Cp(CO)2Fe=C=CR1R2]+TfO-, 3a-c (a, R1, R2 = Me; b, R1 = Ph, R 2 = Me; c, R1, R2 = Ph), isomerize to nonterminal -acetylene complexes, [CP(CO)2Fe(eta2-R1-C=C-R2)]+TfO-, 5a-c, in CD2Cl2 above -50-degrees-C. Carbon-13 labeling and VT 13C NMR are used to track the formation of 3 and its conversion to 5. The isomerizations are intramolecular and apparently irreversible. That of 3b to 5b involves only phenyl migration. It is suggested that Cp(CO)2Fe eta2-acetylenes are favored over CP(CO)2Fe eta1-vinylidenes under these conditions by the strongly electron withdrawing COs which, relative to less pi-acidic ligands, destabilize the vinylidene and stabilize the pi-acetylene.

引用

页码：899 / 905

页数：7

共 87 条

[31] REARRANGEMENT OF A METAL (ETA-2-ALKYNE) COMPLEX TO A METAL VINYLIDENE AND SUBSEQUENT REACTION OF THE METAL VINYLIDENE TO REGENERATE THE ALKYNE [J].