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Sequential migrations between boron and rhodium centers: A cooperative process between rhodium and a monosubstituted borohydride unit

Sequential migrations between boron and rhodium centers: A cooperative process between rhodium and a monosubstituted borohydride unit
Sequential migrations between boron and rhodium centers: A cooperative process between rhodium and a monosubstituted borohydride unit
The sodium salt of a monosubstituted borohydride anion containing a 2-mercaptopyridyl unit (mp) is reported herein. This compound was coordinated to a rhodium(I) center providing the complex [Rh{κ3-H,H,S–H3B(mp)}(NBD)] (1) (where NBD = 2,5-norbornadiene) in which the boron-based ligand is coordinated to the rhodium center via the thione donor and two of the B–H bonds of the BH3 unit. Reaction of complex 1 with carbon monoxide results in the activation of the complex leading to the product of a formal intramolecular hydroboration reaction, where the NBD unit has, in effect, inserted into one of the B–H bonds. Three complexes were prepared in which the newly formed norbornenyl unit (nbe) is located at the boron center, namely, [Rh{κ3-H,H,S–H2B(nbe)(mp)}(CO)2] (2), [Rh{κ3-H,H,S–H2B(nbe)(mp)}(CO)(PCy3)] (3), and [Rh{κ3-H,H,S–H2B(nbe)(mp)}(CO)(PPh3)] (4). The identities of the three complexes were confirmed by spectroscopic and analytical techniques. Further confirmation was obtained via structural characterization of 3. Studies confirmed that the reactivity occurs at the metal center. A metal–ligand cooperative mechanism, involving initial migration of hydride from boron to metal center, was postulated for the formation of the new complexes based on previous investigations. The newly formed norbornenyl unit then migrates from metal center to boron.
0020-1669
446-456
Iannetelli, Angelo
3f6fd91d-6ac8-433e-9e46-1c0831be4ed7
Tizzard, Graham
db9e71fa-1286-41fb-9305-edadc6fa7a89
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Owen, Gareth R.
88a0d18b-a3d5-46f5-b5a8-24c03a5eb66f
Iannetelli, Angelo
3f6fd91d-6ac8-433e-9e46-1c0831be4ed7
Tizzard, Graham
db9e71fa-1286-41fb-9305-edadc6fa7a89
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Owen, Gareth R.
88a0d18b-a3d5-46f5-b5a8-24c03a5eb66f

Iannetelli, Angelo, Tizzard, Graham, Coles, Simon J. and Owen, Gareth R. (2018) Sequential migrations between boron and rhodium centers: A cooperative process between rhodium and a monosubstituted borohydride unit. Inorganic Chemistry, 57 (1), 446-456. (doi:10.1021/acs.inorgchem.7b02700).

Record type: Article

Abstract

The sodium salt of a monosubstituted borohydride anion containing a 2-mercaptopyridyl unit (mp) is reported herein. This compound was coordinated to a rhodium(I) center providing the complex [Rh{κ3-H,H,S–H3B(mp)}(NBD)] (1) (where NBD = 2,5-norbornadiene) in which the boron-based ligand is coordinated to the rhodium center via the thione donor and two of the B–H bonds of the BH3 unit. Reaction of complex 1 with carbon monoxide results in the activation of the complex leading to the product of a formal intramolecular hydroboration reaction, where the NBD unit has, in effect, inserted into one of the B–H bonds. Three complexes were prepared in which the newly formed norbornenyl unit (nbe) is located at the boron center, namely, [Rh{κ3-H,H,S–H2B(nbe)(mp)}(CO)2] (2), [Rh{κ3-H,H,S–H2B(nbe)(mp)}(CO)(PCy3)] (3), and [Rh{κ3-H,H,S–H2B(nbe)(mp)}(CO)(PPh3)] (4). The identities of the three complexes were confirmed by spectroscopic and analytical techniques. Further confirmation was obtained via structural characterization of 3. Studies confirmed that the reactivity occurs at the metal center. A metal–ligand cooperative mechanism, involving initial migration of hydride from boron to metal center, was postulated for the formation of the new complexes based on previous investigations. The newly formed norbornenyl unit then migrates from metal center to boron.

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e-pub ahead of print date: 8 December 2017
Published date: 2 January 2018

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Local EPrints ID: 417362
URI: https://eprints.soton.ac.uk/id/eprint/417362
ISSN: 0020-1669
PURE UUID: f917c9d7-314d-4b6f-8b57-9b4096e5f29a
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 30 Jan 2018 17:30
Last modified: 06 Jun 2018 12:54

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Author: Angelo Iannetelli
Author: Graham Tizzard
Author: Simon J. Coles ORCID iD
Author: Gareth R. Owen

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