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

Reactivity of the bis(pentafluorophenyl)boranes ClB(C6F5)(2) and HB(C6F5)(2) n towards late transition metal reagents
Reactivity of the bis(pentafluorophenyl)boranes ClB(C6F5)(2) and HB(C6F5)(2) n towards late transition metal reagents
The reactivities of the highly electrophilic boranes C1B(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 [(eta(5)-C5R5)Fe(CO)(2)](-) (R = H or Me) and [Mn(CO)(5)](-), leading to the generation of the novel boryl complexes (eta(5)-C5R5)Fe(CO)(2)B(C6F5)(2) [R = H(3) or Me(4)] and (OC)(5)MnB(C6F5)(2) (5). Such systems are designed to probe the extent to which the strongly sigma-donor boryl ligand can also act as a pi-acceptor; a variety of spectroscopic, structural and computational probes imply that even with such strongly electron withdrawing boryl substituents, the pi component of the metal boron linkage is a relatively minor one. Similar reactivity is observed towards the hydridomanganese anion [(eta(5)-C5H4Me)Mn(CO)(2)H](-), generating a thermally labile product identified spectroscopically as (eta(5)-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)(2)Pt(H2C = CH2) ultimately generates EtB(C6F5)(2) (10) as the major boron-containing product, together with cis-(Ph3P)(2)PtCl2 and trans-(Ph3P)(2)Pt(C6F5)Cl (9). The cationic platinum hydride [(Ph3P)(3)PtH](+) is identified as an intermediate in the reaction pathway. Reaction of 2 with [(Ph3P)(2)Rh(mu-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)(2)Rh(eta(6)-C6H5Me)](+) (14) ultimately being formed.
boryl complexes, x-ray, crystal-structure, structural characterization, molecular-structures, oxidative addition, platinum complexes, b bonds, chemistry, boron
1477-9226
4030-4037
Al-Fawaz, Amal
eaa3d55f-f95b-411a-a831-1c272faea6b1
Aldridge, Simon
de66448a-0f63-4b8b-ac55-f78dcd4830ea
Coombs, Deborah L.
4eff45e3-dc89-4545-83d4-0508acda31b7
Dickinson, Anthony A.
b3daf9d2-a910-41f4-b542-1185f2439328
Willock, David J.
d17cca22-472d-4d1b-91a3-e412008a9ca4
Ooi, Li-ling
7c5b6dd6-59d6-4036-8d06-3746602ca1cb
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Al-Fawaz, Amal
eaa3d55f-f95b-411a-a831-1c272faea6b1
Aldridge, Simon
de66448a-0f63-4b8b-ac55-f78dcd4830ea
Coombs, Deborah L.
4eff45e3-dc89-4545-83d4-0508acda31b7
Dickinson, Anthony A.
b3daf9d2-a910-41f4-b542-1185f2439328
Willock, David J.
d17cca22-472d-4d1b-91a3-e412008a9ca4
Ooi, Li-ling
7c5b6dd6-59d6-4036-8d06-3746602ca1cb
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da

Al-Fawaz, Amal, Aldridge, Simon, Coombs, Deborah L., 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), 4030-4037. (doi:10.1039/b414940h).

Record type: Article

Abstract

The reactivities of the highly electrophilic boranes C1B(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 [(eta(5)-C5R5)Fe(CO)(2)](-) (R = H or Me) and [Mn(CO)(5)](-), leading to the generation of the novel boryl complexes (eta(5)-C5R5)Fe(CO)(2)B(C6F5)(2) [R = H(3) or Me(4)] and (OC)(5)MnB(C6F5)(2) (5). Such systems are designed to probe the extent to which the strongly sigma-donor boryl ligand can also act as a pi-acceptor; a variety of spectroscopic, structural and computational probes imply that even with such strongly electron withdrawing boryl substituents, the pi component of the metal boron linkage is a relatively minor one. Similar reactivity is observed towards the hydridomanganese anion [(eta(5)-C5H4Me)Mn(CO)(2)H](-), generating a thermally labile product identified spectroscopically as (eta(5)-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)(2)Pt(H2C = CH2) ultimately generates EtB(C6F5)(2) (10) as the major boron-containing product, together with cis-(Ph3P)(2)PtCl2 and trans-(Ph3P)(2)Pt(C6F5)Cl (9). The cationic platinum hydride [(Ph3P)(3)PtH](+) is identified as an intermediate in the reaction pathway. Reaction of 2 with [(Ph3P)(2)Rh(mu-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)(2)Rh(eta(6)-C6H5Me)](+) (14) ultimately being formed.

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More information

Published date: 2004
Keywords: boryl complexes, x-ray, crystal-structure, structural characterization, molecular-structures, oxidative addition, platinum complexes, b bonds, chemistry, boron

Identifiers

Local EPrints ID: 20114
URI: https://eprints.soton.ac.uk/id/eprint/20114
ISSN: 1477-9226
PURE UUID: c5679292-9084-4a10-ad82-0f0b638346b3
ORCID for Mark E. Light: ORCID iD orcid.org/0000-0002-0585-0843
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 23 Feb 2006
Last modified: 16 Jul 2019 19:07

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