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Preparation and reactivity of rhodium and iridium complexes containing a methylborohydride based unit supported by two 7-azaindolyl heterocycles

Preparation and reactivity of rhodium and iridium complexes containing a methylborohydride based unit supported by two 7-azaindolyl heterocycles
Preparation and reactivity of rhodium and iridium complexes containing a methylborohydride based unit supported by two 7-azaindolyl heterocycles

The synthesis and characterisation of a new anionic flexible scorpionate ligand, methyl(bis-7-azaindolyl)borohydride [MeBai]- is reported herein. The ligand was coordinated to a series of group nine transition metal centres forming the complexes, [Ir(MeBai)(COD)] (1), [Rh(MeBai)(COD)] (2), [Rh(MeBai)(CODMe)] (2-Me) and [Rh(MeBai)(NBD)] (3), where COD = 1,5-cyclooctadiene, CODMe = 3-methyl-1,5-cyclooctadiene and NBD = 2,5-norbornadiene. In all cases, the boron based ligand was found to bind to the metal centres via a κ3-N,N,H coordination mode. The ligand and complexes were fully characterised by spectroscopic and analytical methods. The structures of the ligand and three of the complexes were confirmed by X-ray crystallography. The potential for migration of the "hydride" or "methyl" units from boron to the metal centre was also explored. During these studies an unusual transformation, involving the oxidation of the rhodium centre, was observed in complex 2. In this case, the η4-COD unit transformed into a η13-C8H12 unit where the ring was bound via one sigma bond and one allyl unit. This is the first time such a transformation has been observed at a rhodium centre.

1477-9226
11047-11057
Da Costa, Rosenildo Correa
ce76806a-0dba-4086-99c2-626e9b932c80
Rawe, Benjamin W.
f9ac002b-5ce2-4134-9a42-821b0b843172
Tsoureas, Nikolaos
b40771a1-8870-43bc-8989-3c6eee2f325f
Haddow, Mairi F.
972a735a-f3cd-4352-8afa-d0ea5dd8da03
Sparkes, Hazel A.
9066ec9b-6904-49ac-b650-04d4b5424b73
Tizzard, Graham J.
8474c0fa-40df-43a6-a662-7f3c4722dbf2
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Owen, Gareth R.
88a0d18b-a3d5-46f5-b5a8-24c03a5eb66f
Da Costa, Rosenildo Correa
ce76806a-0dba-4086-99c2-626e9b932c80
Rawe, Benjamin W.
f9ac002b-5ce2-4134-9a42-821b0b843172
Tsoureas, Nikolaos
b40771a1-8870-43bc-8989-3c6eee2f325f
Haddow, Mairi F.
972a735a-f3cd-4352-8afa-d0ea5dd8da03
Sparkes, Hazel A.
9066ec9b-6904-49ac-b650-04d4b5424b73
Tizzard, Graham J.
8474c0fa-40df-43a6-a662-7f3c4722dbf2
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Owen, Gareth R.
88a0d18b-a3d5-46f5-b5a8-24c03a5eb66f

Da Costa, Rosenildo Correa, Rawe, Benjamin W., Tsoureas, Nikolaos, Haddow, Mairi F., Sparkes, Hazel A., Tizzard, Graham J., Coles, Simon J. and Owen, Gareth R. (2018) Preparation and reactivity of rhodium and iridium complexes containing a methylborohydride based unit supported by two 7-azaindolyl heterocycles. Dalton Transactions, 47 (32), 11047-11057. (doi:10.1039/c8dt02311e).

Record type: Article

Abstract

The synthesis and characterisation of a new anionic flexible scorpionate ligand, methyl(bis-7-azaindolyl)borohydride [MeBai]- is reported herein. The ligand was coordinated to a series of group nine transition metal centres forming the complexes, [Ir(MeBai)(COD)] (1), [Rh(MeBai)(COD)] (2), [Rh(MeBai)(CODMe)] (2-Me) and [Rh(MeBai)(NBD)] (3), where COD = 1,5-cyclooctadiene, CODMe = 3-methyl-1,5-cyclooctadiene and NBD = 2,5-norbornadiene. In all cases, the boron based ligand was found to bind to the metal centres via a κ3-N,N,H coordination mode. The ligand and complexes were fully characterised by spectroscopic and analytical methods. The structures of the ligand and three of the complexes were confirmed by X-ray crystallography. The potential for migration of the "hydride" or "methyl" units from boron to the metal centre was also explored. During these studies an unusual transformation, involving the oxidation of the rhodium centre, was observed in complex 2. In this case, the η4-COD unit transformed into a η13-C8H12 unit where the ring was bound via one sigma bond and one allyl unit. This is the first time such a transformation has been observed at a rhodium centre.

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Accepted/In Press date: 13 July 2018
e-pub ahead of print date: 19 July 2018

Identifiers

Local EPrints ID: 425592
URI: http://eprints.soton.ac.uk/id/eprint/425592
ISSN: 1477-9226
PURE UUID: 6a621e76-a707-4058-a316-05c1d3002ca7
ORCID for Graham J. Tizzard: ORCID iD orcid.org/0000-0002-1577-5779
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 25 Oct 2018 16:30
Last modified: 26 Nov 2021 02:45

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Contributors

Author: Rosenildo Correa Da Costa
Author: Benjamin W. Rawe
Author: Nikolaos Tsoureas
Author: Mairi F. Haddow
Author: Hazel A. Sparkes
Author: Simon J. Coles ORCID iD
Author: Gareth R. Owen

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