REACTIONS OF COMPLEX LIGANDS .45. (ACYLAMINO)CARBENE COMPLEXES - SYNTHESIS, STRUCTURE, AND REACTIVITY

被引：56

作者：

GROTJAHN, DB ^{[1
]}

KROLL, FEK ^{[1
]}

SCHAFER, T ^{[1
]}

HARMS, K ^{[1
]}

DOTZ, KH ^{[1
]}

机构：

[1] UNIV MARBURG, FACHBEREICH CHEM, HANS MEERWEIN STR, W-3550 MARBURG, GERMANY

来源：

ORGANOMETALLICS | 1992年 / 11卷 / 01期

关键词：

D O I：

10.1021/om00037a052

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Fischer type aminocarbene complexes of chromium, molybdenum and tungsten undergo N-acylation under DMAP catalysis followed by decarbonylation affording tetracarbonyl ((acylamino)carbene) chelates. These complexes are characterized by a short metal-carbene and a long metal-oxygen bond in the chelate ring. A remarkable chemoselectivity is observed upon reaction with alkynes which is governed by the metal and the N-substitution pattern and which may be rationalized in terms of a stereoselective alkyne insertion into the metal-carbene bond. (CO)4Cr = C(p-Tol)NRCOC(CH3)3 prefers E insertion leading either to carbene annelation (indene, naphthalene derivatives) or to double alkyne insertion products (phenol ester). The molybdenum analogues add the alkyne to give presumed Z-alkenylcarbene intermediates, reasonable precursors for the isolated pyrrol and pyrrolone cycloaddition products.

引用

页码：298 / 310

页数：13

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