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First examples of diazepanylidene carbenes and their late-transition-metal complexes

First examples of diazepanylidene carbenes and their late-transition-metal complexes
First examples of diazepanylidene carbenes and their late-transition-metal complexes
The synthesis of the novel seven-membered N-heterocyclic carbene (NHC) 1,3-dicyclohexyl-1,3-diazepan-2-ylidene (3) and its 5,6-dioxolane derivative 4 is reported and their coordination chemistry with Rh(I), Ir(I), and Pt(0) discussed. The M(cod)(3)Cl, where M = Rh and Ir, complexes display a high rotation barrier at room temperature about the M-CNHC bond, whereas for the M(CO)2(3)Cl and Pt(nbe)2(3) complexes rapid rotation of the carbene ligand is observed at ambient temperature. The infrared (CO) values of the Rh(I) and Ir(I) derivatives M(CO)2(3)Cl give a measure of the donor ability of the new carbene ligands. The crystal structures of the amidinium salts 3·HPF6 and 4·HPF6 together with those of M(cod)(3)Cl [M = Rh, Ir], Ir(cod)(4)Br, Ir(CO)2(3)Cl, and Pt(nbe)2(3) are reported. Both the salts and the coordinated carbene ligands exhibit extremely large NCN angles; for the complexes the angles are in the range 115.5(3) [Pt(3)] to 122(11) [Ir(4)].
iridium(i) complexes, hydrosilylation catalysts, reactivity, rhodium, nhc, ligand properties, phosphine), complexes, alkyl amino carbenes, platinum(0)-carbene, n-heterocyclic carbene
0276-7333
4800-4809
Lglesias, M.
fdc970b3-0d19-437e-a2fe-18cf0ee45071
Beetstra, D.J.
f23e9bcd-1468-461d-9349-80c3bcd2d05e
Stasch, A.
4d98a151-ce03-44a4-9e2a-7dd9f7692751
Horton, P.N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Hursthouse, M.B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Cavell, K.J.
dc584567-b516-4669-a539-209d2fe5557d
Dervisi, A.
1e212a42-799c-460d-aea8-754b03da08ab
Fallis, I.A.
1cfad371-2ca4-46c0-a28b-f2cf528446c1
Lglesias, M.
fdc970b3-0d19-437e-a2fe-18cf0ee45071
Beetstra, D.J.
f23e9bcd-1468-461d-9349-80c3bcd2d05e
Stasch, A.
4d98a151-ce03-44a4-9e2a-7dd9f7692751
Horton, P.N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Hursthouse, M.B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Cavell, K.J.
dc584567-b516-4669-a539-209d2fe5557d
Dervisi, A.
1e212a42-799c-460d-aea8-754b03da08ab
Fallis, I.A.
1cfad371-2ca4-46c0-a28b-f2cf528446c1

Lglesias, M., Beetstra, D.J., Stasch, A., Horton, P.N., Hursthouse, M.B., Coles, S.J., Cavell, K.J., Dervisi, A. and Fallis, I.A. (2007) First examples of diazepanylidene carbenes and their late-transition-metal complexes. Organometallics, 26 (19), 4800-4809. (doi:10.1021/om7004904).

Record type: Article

Abstract

The synthesis of the novel seven-membered N-heterocyclic carbene (NHC) 1,3-dicyclohexyl-1,3-diazepan-2-ylidene (3) and its 5,6-dioxolane derivative 4 is reported and their coordination chemistry with Rh(I), Ir(I), and Pt(0) discussed. The M(cod)(3)Cl, where M = Rh and Ir, complexes display a high rotation barrier at room temperature about the M-CNHC bond, whereas for the M(CO)2(3)Cl and Pt(nbe)2(3) complexes rapid rotation of the carbene ligand is observed at ambient temperature. The infrared (CO) values of the Rh(I) and Ir(I) derivatives M(CO)2(3)Cl give a measure of the donor ability of the new carbene ligands. The crystal structures of the amidinium salts 3·HPF6 and 4·HPF6 together with those of M(cod)(3)Cl [M = Rh, Ir], Ir(cod)(4)Br, Ir(CO)2(3)Cl, and Pt(nbe)2(3) are reported. Both the salts and the coordinated carbene ligands exhibit extremely large NCN angles; for the complexes the angles are in the range 115.5(3) [Pt(3)] to 122(11) [Ir(4)].

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More information

Published date: 2007
Keywords: iridium(i) complexes, hydrosilylation catalysts, reactivity, rhodium, nhc, ligand properties, phosphine), complexes, alkyl amino carbenes, platinum(0)-carbene, n-heterocyclic carbene

Identifiers

Local EPrints ID: 54335
URI: http://eprints.soton.ac.uk/id/eprint/54335
ISSN: 0276-7333
PURE UUID: 75404a93-f49f-49bb-b050-f5eeacc10529
ORCID for P.N. Horton: ORCID iD orcid.org/0000-0001-8886-2016
ORCID for S.J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 31 Jul 2008
Last modified: 16 Mar 2024 03:12

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Contributors

Author: M. Lglesias
Author: D.J. Beetstra
Author: A. Stasch
Author: P.N. Horton ORCID iD
Author: M.B. Hursthouse
Author: S.J. Coles ORCID iD
Author: K.J. Cavell
Author: A. Dervisi
Author: I.A. Fallis

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