Reactivity of the bis(pentafluorophenyl)boranes ClB(C6F5)2 and [HB(C6F5)2]n towards late transition metal reagents

Al-Fawaz, Amal, Aldridge, Simon, Coombs, Deborah L. ORCID: https://orcid.org/0000-0002-4616-6001, Dickinson, Anthony A., Willock, David J., Ooi, Li-ling, Light, Mark E., Coles, Simon J. and Hursthouse, Michael B. 2004. Reactivity of the bis(pentafluorophenyl)boranes ClB(C6F5)2 and [HB(C6F5)2]n towards late transition metal reagents. Dalton Transactions (23) , pp. 4030-4037. 10.1039/b414940h

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Abstract

The reactivities of the highly electrophilic boranes ClB(C6F5)2 (1) and [HB(C6F5)2]n (2) towards a range of organometallic reagents featuring metals from Groups 7–10 have been investigated. Salt elimination chemistry is observed between 1 and the nucleophilic anions [(η5-C5R5)Fe(CO)2]− (R = H or Me) and [Mn(CO)5]−, leading to the generation of the novel boryl complexes (η5-C5R5)Fe(CO)2B(C6F5)2 [R = H (3) or Me (4)] and (OC)5MnB(C6F5)2 (5). Such systems are designed to probe the extent to which the strongly σ-donor boryl ligand can also act as a π-acceptor; a variety of spectroscopic, structural and computational probes imply that even with such strongly electron withdrawing boryl substituents, the π component of the metal–boron linkage is a relatively minor one. Similar reactivity is observed towards the hydridomanganese anion [(η5-C5H4Me)Mn(CO)2H]−, generating a thermally labile product identified spectroscopically as (η5-C5H4Me)Mn(CO)2(H)B(C6F5)2 (6). Boranes 1 and 2 display different patterns of reactivity towards low-valent platinum and rhodium complexes than those demonstrated previously for less electrophilic reagents. Thus, reaction of 1 with (Ph3P)2Pt(H2C[double bond, length as m-dash]CH2) ultimately generates EtB(C6F5)2 (10) as the major boron-containing product, together with cis-(Ph3P)2PtCl2 and trans-(Ph3P)2Pt(C6F5)Cl (9). The cationic platinum hydride [(Ph3P)3PtH]+ is identified as an intermediate in the reaction pathway. Reaction of 2 with [(Ph3P)2Rh(µ-Cl)]2, in toluene on the other hand, appears to proceed via ligand abstraction with both Ph3P·HB(C6F5)2 (11) and the arene rhodium(I) cation [(Ph3P)2Rh(η6-C6H5Me)]+ (14) ultimately being formed.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Schools > Chemistry
Publisher:	Royal Society of Chemistry
ISSN:	1477-9226
Last Modified:	12 Jul 2024 13:46
URI:	https://orca.cardiff.ac.uk/id/eprint/170533

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