A mechanistic study of the C-P bond cleavage reaction of 1,2-(PH 2)2-C6H4 with nBuLi/ Sb(NMe2)3

Ruth Edge; Robert J. Less; Vesal Naseri; Eric J L McInnes; Robert E. Mulvey; Dominic S. Wright

doi:10.1039/b810028d

A mechanistic study of the C-P bond cleavage reaction of 1,2-(PH 2)2-C6H4 with nBuLi/ Sb(NMe2)3

Ruth Edge, Robert J. Less, Vesal Naseri, Eric J L McInnes, Robert E. Mulvey, Dominic S. Wright

Research output: Contribution to journal › Article › peer-review

Abstract

In situ 31P NMR spectroscopic studies of the reaction of the primary diphosphine 1,2-(PH2)2-C6H4 with the mixed-metal base system nBuLi/Sb(NMe2) 3, combined with X-ray structural investigations, strongly support a mechanism involving a series of deprotonation steps followed by antimony-mediated reductive C-P bond cleavage. The central intermediate in this reaction is the tetraphosphide dianion [C6H4P 2]22- ([4]) from which the final products, the 1,2,3-triphospholide anion [C6H4P3]- (3) and [PhPHLi] (8·Li), are evolved. An EPR spectrocopic study suggests that homolytic C-P bond cleavage is likely to be involved in this final step. © 2008 The Royal Society of Chemistry.

Original language	English
Pages (from-to)	6454-6460
Number of pages	6
Journal	Dalton Transactions
Issue number	45
DOIs	https://doi.org/10.1039/b810028d
Publication status	Published - 2008

Keywords

ZINTL COMPOUNDS
E(NME2)(3) E
ANIONS
PHOSPHORUS
RADICALS
SB

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10.1039/b810028d

CCDC 691463: Experimental Crystal Structure Determination
Edge, R. (Contributor), Less, R. J. (Contributor), Naseri, V. (Contributor), Mcinnes, E. (Contributor), Mulvey, R. E. (Contributor) & Wright, D. S. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2009
DOI: 10.5517/ccr6j8q, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccr6j8q&sid=DataCite
Dataset
CCDC 691462: Experimental Crystal Structure Determination
Edge, R. (Contributor), Less, R. J. (Contributor), Naseri, V. (Contributor), Mcinnes, E. (Contributor), Mulvey, R. E. (Contributor) & Wright, D. S. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2009
DOI: 10.5517/ccr6j7p, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccr6j7p&sid=DataCite
Dataset

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@article{fbf91c69124141c5af8ee174b091d101,

title = "A mechanistic study of the C-P bond cleavage reaction of 1,2-(PH 2)2-C6H4 with nBuLi/ Sb(NMe2)3",

abstract = "In situ 31P NMR spectroscopic studies of the reaction of the primary diphosphine 1,2-(PH2)2-C6H4 with the mixed-metal base system nBuLi/Sb(NMe2) 3, combined with X-ray structural investigations, strongly support a mechanism involving a series of deprotonation steps followed by antimony-mediated reductive C-P bond cleavage. The central intermediate in this reaction is the tetraphosphide dianion [C6H4P 2]22- ([4]) from which the final products, the 1,2,3-triphospholide anion [C6H4P3]- (3) and [PhPHLi] (8·Li), are evolved. An EPR spectrocopic study suggests that homolytic C-P bond cleavage is likely to be involved in this final step. {\textcopyright} 2008 The Royal Society of Chemistry.",

keywords = "ZINTL COMPOUNDS, E(NME2)(3) E, ANIONS, PHOSPHORUS, RADICALS, SB",

author = "Ruth Edge and Less, {Robert J.} and Vesal Naseri and McInnes, {Eric J L} and Mulvey, {Robert E.} and Wright, {Dominic S.}",

note = "Edge, Ruth Less, Robert J. Naseri, Vesal McInnes, Eric J. L. Mulvey, Robert E. Wright, Dominic S. EPSRC We gratefully acknowledge the EPSRC ( R. E., R. J. L., V. N., E. J. L. M., R. E. M., D. S. W.) for financial support. 28 ROYAL SOC CHEMISTRY CAMBRIDGE 371ME",

year = "2008",

doi = "10.1039/b810028d",

language = "English",

pages = "6454--6460",

journal = "Dalton Transactions",

issn = "1477-9234",

publisher = "Royal Society of Chemistry",

number = "45",

}

TY - JOUR

T1 - A mechanistic study of the C-P bond cleavage reaction of 1,2-(PH 2)2-C6H4 with nBuLi/ Sb(NMe2)3

AU - Edge, Ruth

AU - Less, Robert J.

AU - Naseri, Vesal

AU - McInnes, Eric J L

AU - Mulvey, Robert E.

AU - Wright, Dominic S.

N1 - Edge, Ruth Less, Robert J. Naseri, Vesal McInnes, Eric J. L. Mulvey, Robert E. Wright, Dominic S. EPSRC We gratefully acknowledge the EPSRC ( R. E., R. J. L., V. N., E. J. L. M., R. E. M., D. S. W.) for financial support. 28 ROYAL SOC CHEMISTRY CAMBRIDGE 371ME

PY - 2008

Y1 - 2008

N2 - In situ 31P NMR spectroscopic studies of the reaction of the primary diphosphine 1,2-(PH2)2-C6H4 with the mixed-metal base system nBuLi/Sb(NMe2) 3, combined with X-ray structural investigations, strongly support a mechanism involving a series of deprotonation steps followed by antimony-mediated reductive C-P bond cleavage. The central intermediate in this reaction is the tetraphosphide dianion [C6H4P 2]22- ([4]) from which the final products, the 1,2,3-triphospholide anion [C6H4P3]- (3) and [PhPHLi] (8·Li), are evolved. An EPR spectrocopic study suggests that homolytic C-P bond cleavage is likely to be involved in this final step. © 2008 The Royal Society of Chemistry.

AB - In situ 31P NMR spectroscopic studies of the reaction of the primary diphosphine 1,2-(PH2)2-C6H4 with the mixed-metal base system nBuLi/Sb(NMe2) 3, combined with X-ray structural investigations, strongly support a mechanism involving a series of deprotonation steps followed by antimony-mediated reductive C-P bond cleavage. The central intermediate in this reaction is the tetraphosphide dianion [C6H4P 2]22- ([4]) from which the final products, the 1,2,3-triphospholide anion [C6H4P3]- (3) and [PhPHLi] (8·Li), are evolved. An EPR spectrocopic study suggests that homolytic C-P bond cleavage is likely to be involved in this final step. © 2008 The Royal Society of Chemistry.

KW - ZINTL COMPOUNDS

KW - E(NME2)(3) E

KW - ANIONS

KW - PHOSPHORUS

KW - RADICALS

KW - SB

U2 - 10.1039/b810028d

DO - 10.1039/b810028d

M3 - Article

SN - 1477-9234

SP - 6454

EP - 6460

JO - Dalton Transactions

JF - Dalton Transactions

IS - 45

ER -

A mechanistic study of the C-P bond cleavage reaction of 1,2-(PH 2)2-C6H4 with nBuLi/ Sb(NMe2)3

Abstract

Keywords

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Datasets

CCDC 691463: Experimental Crystal Structure Determination

CCDC 691462: Experimental Crystal Structure Determination

Cite this