Spontaneous dehydrocoupling in peri-substituted phosphine-borane adducts

Laurence John Taylor; Brian Andrew Surgenor; Piotr Wawrzyniak; Matthew James Ray; David Bradford Cordes; Alexandra Martha Zoya Slawin; Petr Kilian

doi:10.1039/C5DT02539G

Spontaneous dehydrocoupling in peri-substituted phosphine-borane adducts

Laurence John Taylor, Brian Andrew Surgenor, Piotr Wawrzyniak, Matthew James Ray, David Bradford Cordes, Alexandra Martha Zoya Slawin, Petr Kilian

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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.

Original language	English
Pages (from-to)	1976-1986
Journal	Dalton Transactions
Volume	45
Issue number	5
Early online date	21 Aug 2015
DOIs	https://doi.org/10.1039/C5DT02539G
Publication status	Published - 7 Feb 2016

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Kilian_2015_DT_Spontaneous_CC
Copyright 2015 the Authors. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (http://creativecommons.org/licenses/by/3.0/).
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Cite this

@article{5ed7b004c7b4406daa61488727ad04bc,

title = "Spontaneous dehydrocoupling in peri-substituted phosphine-borane adducts",

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.",

author = "Taylor, {Laurence John} and Surgenor, {Brian Andrew} and Piotr Wawrzyniak and Ray, {Matthew James} and Cordes, {David Bradford} and Slawin, {Alexandra Martha Zoya} and Petr Kilian",

note = "This work was financially supported by the EPSRC and COST action CM1302 SIPs. ",

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AU - Surgenor, Brian Andrew

AU - Wawrzyniak, Piotr

AU - Ray, Matthew James

AU - Cordes, David Bradford

AU - Slawin, Alexandra Martha Zoya

AU - Kilian, Petr

N1 - This work was financially supported by the EPSRC and COST action CM1302 SIPs.

PY - 2016/2/7

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N2 - 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.

AB - 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.

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U2 - 10.1039/C5DT02539G

DO - 10.1039/C5DT02539G

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SN - 1477-9226

VL - 45

SP - 1976

EP - 1986

JO - Dalton Transactions

JF - Dalton Transactions

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Spontaneous dehydrocoupling in peri-substituted phosphine-borane adducts

Abstract

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EP/E010395/1 STABLE PHOSPHORUS CENTRED: Stable Phosphorous Cenred Radicals and Odd Electron Bonds

Petr Kilian