The (η6-benzene)Cr(CO)3-substituted propargyl cation:: Spectroscopic characterization and reactions of an ambident electrophile

被引：18

作者：

Muller, TJJ ^{[1
]}

Netz, AA ^{[1
]}

机构：

[1] Univ Munich, Inst Organ Chem, D-80333 Munchen, Germany

来源：

ORGANOMETALLICS | 1998年 / 17卷 / 16期

关键词：

D O I：

10.1021/om980257u

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

An (arene)Cr(CO)(3)-stabilized propargyl cation can be easily generated upon ionization of the propargyl acetate Cr(CO)(3)(eta(6)-C6H5)CH(OC(O)CH3)C = CPh with boron trifluoride. The structure investigation of this pi-complex stabilized ambident electrophile by NMR spectroscopy and extended Huckel calculations reveals that the charge density in the propargylic position is higher than in the allenylic position. The rapid formation of the cation can be followed by measuring the UV/vis kinetics for the ionization of the acetate. The cationic species reacts with alcohols to give exclusively propargyl ethers Cr(CO)(3)(eta(6)-C6H5)CH(OR)C= CPh and with thiols to give regioselectively allenyl thioethers Cr(CO)(3)(eta(6)-C6H5)CH=C=C(SR)Ph.

引用

页码：3609 / 3614

页数：6

共 41 条

[31]

Murray M, 1977, METHODEN HERSTELLUNG, V5, P991

[32] CHEMISTRY AND SYNTHETIC UTILITY OF COBALT-COMPLEXED PROPARGYL CATIONS [J].

NICHOLAS, KM .

ACCOUNTS OF CHEMICAL RESEARCH, 1987, 20 (06) :207-214

[33] CHEMISTRY AND BIOLOGY OF THE ENEDIYNE ANTICANCER ANTIBIOTICS [J].

NICOLAOU, KC ;

DAI, WM .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1991, 30 (11) :1387-1416

[34] STABLE CARBOCATIONS .173. C-13 NUCLEAR MAGNETIC-RESONANCE STUDIES OF ALKYNYLCARBENIUM IONS AND ALKYNOYL CATIONS - RELATIVE IMPORTANCE OF MESOMERIC VINYLIC (ALLENYLIC) CATION FORMS [J].

OLAH, GA ;

SPEAR, RJ ;

WESTERMA.PW ;

DENIS, JM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1974, 96 (18) :5855-5859

[35] ORGANOMETALLIC CHEMISTRY .9. C-13 NUCLEAR MAGNETIC-RESONANCE STUDY OF CUMYLCHROMIUM TRICARBONYL AND OF CYCLOHEPTATRIENYLMOLYBDENUM (CYCLOHEPTATRIENYLCHROMIUM, AND CYCLOHEPTATRIENYLTUNGSTEN) TRICARBONYL CATIONS [J].

OLAH, GA ;

YU, SH .

JOURNAL OF ORGANIC CHEMISTRY, 1976, 41 (10) :1694-1697

[36] CARBONIUM-ION STABILIZATION BY (ETA-5-CYCLOPENTADIENYL)DICARBONYLNITROSYLCHROMIUM - A H-1 AND C-13 NMR-STUDY [J].

RAUSCH, MD ;

KOWALSKI, DJ ;

MINTZ, EA .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1988, 342 (02) :201-208

[37] METAL-STABILIZED CARBONIUM-IONS DERIVED FROM BIS(TRICARBONYLCHROMIUM) COMPLEXES OF DIARYLMETHANES [J].

SEYFERTH, D ;

MEROLA, JS ;

ESCHBACH, CS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (13) :4124-4131

[38]

SOLLADIECAVALLO A, 1985, POLYHEDRON, V4, P910

[39]

Team of authors, 1993, ORGANIKUM

[40] ARENE-METAL COMPLEXES .I. THERMODYNAMIC STABILITIES OF SUBSTITUTED BENZYL CATIONS COMPLEXED WITH TRICARBONYLCHROMIUM [J].

TRAHANOVSKY, WS ;

WELLS, DK .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1969, 91 (21) :5870-+

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