Formation of tungsten ethylidene complexes from diethyl complexes through a proton-catalyzed rearrangement of ethylene

W(NAr)<sub>2</sub>Et<sub>2</sub> (Ar = 2,6-diisopropylphenyl) reacts with two equivalents of R<sub>F9</sub>OH (OR<sub>F9</sub> = OC(CF<sub>3</sub>)<sub>3</sub>) to yield W(NAr)(ArNH<sub>2</sub>)(OR<sub>F9</sub>)<sub>2</sub>(C<sub>2</sub>H<sub>4</sub>) complexes and ethane. In solution W(NAr)(ArNH<sub>2</sub>)(OR<sub>F9</sub>)<sub>2</sub>(C<sub>2</sub>H<sub>4</sub>) decomposes to give R<sub>F9</sub>OH, ethane, W(NAr)(OR<sub>F9</sub>)<sub>2</sub>(C<sub>2</sub>H<sub>4</sub>), and W(NAr)(NHAr')(ArNH<sub>2</sub>)(OR<sub>F9</sub>), in which Ar' contains a dehydrogenated isopropyl group (Ar' = (2-i-Pr)(6-CMe[double bond, length as m-dash]CH<sub>2</sub>)C<sub>6</sub>H<sub>3</sub>) coordinated to the metal. On a similar time scale W(NAr)(OR<sub>F9</sub>)<sub>2</sub>(CHCH<sub>3</sub>) complexes are formed from W(NAr)(OR<sub>F9</sub>)<sub>2</sub>(C<sub>2</sub>H<sub>4</sub>) through an ArNH<sub>2</sub>-catalyzed rearrangement of the ethylene ligand. W(NAr)(NHAr')(ArNH<sub>2</sub>)(OR<sub>F9</sub>) reacts with cyclohexene to form methylenecyclohexene and complexes that contain an NHAr″ ligand where Ar″ is a disubstituted (methyl/aryl) alkylidene, (2-i-Pr)(6-CMe)C<sub>6</sub>H<sub>3</sub>) that is tethered to the metal through the amido nitrogen. In contrast to W(NAr)(ArNH<sub>2</sub>)(OR<sub>F9</sub>)<sub>2</sub>(C<sub>2</sub>H<sub>4</sub>), analogous OR<sub>F6</sub> (OCMe(CF<sub>3</sub>)<sub>2</sub>) and OR<sub>F3</sub> (OCMe<sub>2</sub>(CF<sub>3</sub>)) complexes are relatively stable at 22 °C.

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Journal
Chemical Science
Published
2025-11-12
DOI
https://doi.org/10.1039/d5sc07302b
Primary Topic
Organometallic Complex Synthesis and Catalysis
Type
article
Field-Weighted Citation Impact
0.00

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article

Formation of tungsten ethylidene complexes from diethyl complexes through a proton-catalyzed rearrangement of ethylene

Matthew P. Conley, Milan Maji, Veronica Carta, Richard R. Schrock et al.
Chemical Science
Organometallic Complex Synthesis and Catalysis
article

Formation of tungsten ethylidene complexes from diethyl complexes through a proton-catalyzed rearrangement of ethylene

Matthew P. Conley, Milan Maji, Veronica Carta, Richard R. Schrock, L. Zeng
article en

Abstract

W(NAr)<sub>2</sub>Et<sub>2</sub> (Ar = 2,6-diisopropylphenyl) reacts with two equivalents of R<sub>F9</sub>OH (OR<sub>F9</sub> = OC(CF<sub>3</sub>)<sub>3</sub>) to yield W(NAr)(ArNH<sub>2</sub>)(OR<sub>F9</sub>)<sub>2</sub>(C<sub>2</sub>H<sub>4</sub>) complexes and ethane. In solution W(NAr)(ArNH<sub>2</sub>)(OR<sub>F9</sub>)<sub>2</sub>(C<sub>2</sub>H<sub>4</sub>) decomposes to give R<sub>F9</sub>OH, ethane, W(NAr)(OR<sub>F9</sub>)<sub>2</sub>(C<sub>2</sub>H<sub>4</sub>), and W(NAr)(NHAr')(ArNH<sub>2</sub>)(OR<sub>F9</sub>), in which Ar' contains a dehydrogenated isopropyl group (Ar' = (2-i-Pr)(6-CMe[double bond, length as m-dash]CH<sub>2</sub>)C<sub>6</sub>H<sub>3</sub>) coordinated to the metal. On a similar time scale W(NAr)(OR<sub>F9</sub>)<sub>2</sub>(CHCH<sub>3</sub>) complexes are formed from W(NAr)(OR<sub>F9</sub>)<sub>2</sub>(C<sub>2</sub>H<sub>4</sub>) through an ArNH<sub>2</sub>-catalyzed rearrangement of the ethylene ligand. W(NAr)(NHAr')(ArNH<sub>2</sub>)(OR<sub>F9</sub>) reacts with cyclohexene to form methylenecyclohexene and complexes that contain an NHAr″ ligand where Ar″ is a disubstituted (methyl/aryl) alkylidene, (2-i-Pr)(6-CMe)C<sub>6</sub>H<sub>3</sub>) that is tethered to the metal through the amido nitrogen. In contrast to W(NAr)(ArNH<sub>2</sub>)(OR<sub>F9</sub>)<sub>2</sub>(C<sub>2</sub>H<sub>4</sub>), analogous OR<sub>F6</sub> (OCMe(CF<sub>3</sub>)<sub>2</sub>) and OR<sub>F3</sub> (OCMe<sub>2</sub>(CF<sub>3</sub>)) complexes are relatively stable at 22 °C.

Chemical ScienceVol. 17(1)
University of California, Riverside (US)
U.S. Department of Energy, Basic Energy Sciences
Openalex Percentile: Top 74%
Organometallic Complex Synthesis and Catalysis
DOIOpen Access PDFOpenAlex
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