Efficient catalytic alkyne metathesis with a fluoroalkoxy-supported ditungsten(III) complex

The molybdenum and tungsten complexes M2(OR)6 (Mo2F6, M = Mo, R = C(CF3)2Me; W2F3, M = W, R = OC(CF3)Me2) were synthesized as bimetallic congeners of the highly active alkyne metathesis catalysts [MesC≡M{OC(CF3)nMe3−n}] (MoF6, M = Mo, n = 2; WF3, M = W, n = 1; Mes = 2,4,6-trimethylphenyl). The corre...

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Main Authors: Henrike Ehrhorn, Janin Schlösser, Dirk Bockfeld, Matthias Tamm
Format: Article
Language:English
Published: Beilstein-Institut 2018-09-01
Series:Beilstein Journal of Organic Chemistry
Subjects:
Online Access:https://doi.org/10.3762/bjoc.14.220
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spelling doaj-cf52c3b067cd4d71b81acdb1adfe2a612021-02-02T00:30:42ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972018-09-011412425243410.3762/bjoc.14.2201860-5397-14-220Efficient catalytic alkyne metathesis with a fluoroalkoxy-supported ditungsten(III) complexHenrike Ehrhorn0Janin Schlösser1Dirk Bockfeld2Matthias Tamm3Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, GermanyInstitut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, GermanyInstitut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, GermanyInstitut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, GermanyThe molybdenum and tungsten complexes M2(OR)6 (Mo2F6, M = Mo, R = C(CF3)2Me; W2F3, M = W, R = OC(CF3)Me2) were synthesized as bimetallic congeners of the highly active alkyne metathesis catalysts [MesC≡M{OC(CF3)nMe3−n}] (MoF6, M = Mo, n = 2; WF3, M = W, n = 1; Mes = 2,4,6-trimethylphenyl). The corresponding benzylidyne complex [PhC≡W{OC(CF3)Me2}] (WPhF3) was prepared by cleaving the W≡W bond in W2F3 with 1-phenyl-1-propyne. The catalytic alkyne metathesis activity of these metal complexes was determined in the self-metathesis, ring-closing alkyne metathesis and cross-metathesis of internal and terminal alkynes, revealing an almost equally high metathesis activity for the bimetallic tungsten complex W2F3 and the alkylidyne complex WPhF3. In contrast, Mo2F6 displayed no significant activity in alkyne metathesis.https://doi.org/10.3762/bjoc.14.220alkylidyne complexesalkyne metathesiscatalysisterminal alkynestungsten
collection DOAJ
language English
format Article
sources DOAJ
author Henrike Ehrhorn
Janin Schlösser
Dirk Bockfeld
Matthias Tamm
spellingShingle Henrike Ehrhorn
Janin Schlösser
Dirk Bockfeld
Matthias Tamm
Efficient catalytic alkyne metathesis with a fluoroalkoxy-supported ditungsten(III) complex
Beilstein Journal of Organic Chemistry
alkylidyne complexes
alkyne metathesis
catalysis
terminal alkynes
tungsten
author_facet Henrike Ehrhorn
Janin Schlösser
Dirk Bockfeld
Matthias Tamm
author_sort Henrike Ehrhorn
title Efficient catalytic alkyne metathesis with a fluoroalkoxy-supported ditungsten(III) complex
title_short Efficient catalytic alkyne metathesis with a fluoroalkoxy-supported ditungsten(III) complex
title_full Efficient catalytic alkyne metathesis with a fluoroalkoxy-supported ditungsten(III) complex
title_fullStr Efficient catalytic alkyne metathesis with a fluoroalkoxy-supported ditungsten(III) complex
title_full_unstemmed Efficient catalytic alkyne metathesis with a fluoroalkoxy-supported ditungsten(III) complex
title_sort efficient catalytic alkyne metathesis with a fluoroalkoxy-supported ditungsten(iii) complex
publisher Beilstein-Institut
series Beilstein Journal of Organic Chemistry
issn 1860-5397
publishDate 2018-09-01
description The molybdenum and tungsten complexes M2(OR)6 (Mo2F6, M = Mo, R = C(CF3)2Me; W2F3, M = W, R = OC(CF3)Me2) were synthesized as bimetallic congeners of the highly active alkyne metathesis catalysts [MesC≡M{OC(CF3)nMe3−n}] (MoF6, M = Mo, n = 2; WF3, M = W, n = 1; Mes = 2,4,6-trimethylphenyl). The corresponding benzylidyne complex [PhC≡W{OC(CF3)Me2}] (WPhF3) was prepared by cleaving the W≡W bond in W2F3 with 1-phenyl-1-propyne. The catalytic alkyne metathesis activity of these metal complexes was determined in the self-metathesis, ring-closing alkyne metathesis and cross-metathesis of internal and terminal alkynes, revealing an almost equally high metathesis activity for the bimetallic tungsten complex W2F3 and the alkylidyne complex WPhF3. In contrast, Mo2F6 displayed no significant activity in alkyne metathesis.
topic alkylidyne complexes
alkyne metathesis
catalysis
terminal alkynes
tungsten
url https://doi.org/10.3762/bjoc.14.220
work_keys_str_mv AT henrikeehrhorn efficientcatalyticalkynemetathesiswithafluoroalkoxysupportedditungsteniiicomplex
AT janinschlosser efficientcatalyticalkynemetathesiswithafluoroalkoxysupportedditungsteniiicomplex
AT dirkbockfeld efficientcatalyticalkynemetathesiswithafluoroalkoxysupportedditungsteniiicomplex
AT matthiastamm efficientcatalyticalkynemetathesiswithafluoroalkoxysupportedditungsteniiicomplex
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