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Spontaneous dehydrocoupling in peri-substituted phosphine-borane adducts

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Kilian_2015_DT_Spontaneous_CC.pdf (993.3Kb)
Date
07/02/2016
Author
Taylor, Laurence John
Surgenor, Brian Andrew
Wawrzyniak, Piotr
Ray, Matthew James
Cordes, David Bradford
Slawin, Alexandra Martha Zoya
Kilian, Petr
Funder
EPSRC
Grant ID
EP/E010695/1
Keywords
QD Chemistry
DAS
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Abstract
Bis(borane) adducts Acenap(PiPr2·BH3)(PRH·BH3) (Acenap = acenaphthene-5,6-diyl; 4a, R = Ph; 4b, R = ferrocenyl, Fc; 4c, R = H) were synthesised by the reaction of excess H3B·SMe2 with either phosphino-phosphonium salts [Acenap(PiPr2)(PR)]+Cl− (1a, R = Ph; 1b, R = Fc), or bis(phosphine) Acenap(PiPr2)(PH2) (3). Bis(borane) adducts 4a–c were found to undergo dihydrogen elimination at room temperature, this spontaneous catalyst-free phosphine-borane dehydrocoupling yields BH2 bridged species Acenap(PiPr2)(µ-BH2)(PR·BH3) (5a, R = Ph; 5b, R = Fc; 5c, R = H). Thermolysis of 5c results in loss of the terminal borane moiety to afford Acenap(PiPr2)(µ-BH2)(PH) (14). Single crystal X-ray structures of 3, 4b and 5a–c are reported.
Citation
Taylor , L J , Surgenor , B A , Wawrzyniak , P , Ray , M J , Cordes , D B , Slawin , A M Z & Kilian , P 2016 , ' Spontaneous dehydrocoupling in peri -substituted phosphine-borane adducts ' , Dalton Transactions , vol. 45 , no. 5 , pp. 1976-1986 . https://doi.org/10.1039/C5DT02539G
Publication
Dalton Transactions
Status
Peer reviewed
DOI
https://doi.org/10.1039/C5DT02539G
ISSN
1477-9226
Type
Journal article
Rights
Copyright 2015 the Authors. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (http://creativecommons.org/licenses/by/3.0/).
Description
This work was financially supported by the EPSRC and COST action CM1302 SIPs.
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  • University of St Andrews Research
URL
http://www.rsc.org/suppdata/c5/dt/c5dt02539g/c5dt02539g1.cif
URI
http://hdl.handle.net/10023/7806

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