Synthesis and structural characterisation of rhodium hydride complexes bearing N-heterocyclic carbene ligands

Susie Douglas; John P. Lowe; Mary F. Mahon; John E. Warren; Michael K. Whittlesey

doi:10.1016/j.jorganchem.2005.02.017

Synthesis and structural characterisation of rhodium hydride complexes bearing N-heterocyclic carbene ligands

Susie Douglas, John P. Lowe, Mary F. Mahon, John E. Warren, Michael K. Whittlesey

Research output: Contribution to journal › Article › peer-review

Abstract

Addition of excesses of N-heterocyclic carbenes (NHCs) IEt 2Me2, IiPr2Me2 or ICy (IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene; IiPr2Me2 = 1,3-diisopropyl-4,5- dimethylimidazol-2-ylidene; ICy = 1,3-dicyclohexylimidazol-2-ylidene) to [HRh(PPh3)4] (1) affords an isomeric mixture of [HRh(NHC)(PPh3)2] (NHC = IEt2Me2 (cis-/trans-2), IiPr2Me2 (cis-/trans-3), ICy (cis-/trans-4) and [HRh(NHC)2(PPh3)] (IEt 2Me2(cis-/trans-5), IiPr2Me 2 (cis-/trans-6), ICy (cis-/trans-7)). Thermolysis of 1 with the aryl substituted NHC, 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene (IMesH 2), affords the bridging hydrido phosphido dimer, [{(PPh 3)2Rh}2(μ-H)(μ-PPh2)] (8), which is also the reaction product formed in the absence of carbene. When the rhodium precursor was changed from 1 to [HRh(CO)(PPh3)3] (9) and treated with either IMes (=1,3-dimesitylimidazol-2-ylidene) or ICy, the bis-NHC complexes trans-[HRh(CO)(IMes)2] (10) and trans-[HRh(CO)(ICy)2] (11) were formed. In contrast, the reaction of 9 with IiPr2Me2 gave [HRh(CO)(I iPr2Me2)2] (cis-/trans-12) and the unusual unsymmetrical dimer, [(PPh3)2Rh(μ-CO) 2Rh(IiPr2Me2)2] (13). The complexes trans-3, 8, 10 and 13 have been structurally characterised. © 2005 Elsevier B.V. All rights reserved.

Original language	English
Pages (from-to)	5027-5035
Number of pages	8
Journal	Journal of Organometallic Chemistry
Volume	690
Issue number	23
DOIs	https://doi.org/10.1016/j.jorganchem.2005.02.017
Publication status	Published - 15 Nov 2005

Keywords

Hydride ligands
N-heterocyclic carbenes
Rhodium complexes

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10.1016/j.jorganchem.2005.02.017

CCDC 260102: Experimental Crystal Structure Determination
Douglas, S. (Contributor), Lowe, J. P. (Contributor), Mahon, M. F. (Contributor), Warren, J. (Contributor) & Whittlesey, M. K. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2006
DOI: 10.5517/cc8qnd0, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc8qnd0&sid=DataCite
Dataset
CCDC 260100: Experimental Crystal Structure Determination
Douglas, S. (Contributor), Lowe, J. P. (Contributor), Mahon, M. F. (Contributor), Warren, J. (Contributor) & Whittlesey, M. K. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2006
DOI: 10.5517/cc8qnby, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc8qnby&sid=DataCite
Dataset
CCDC 260103: Experimental Crystal Structure Determination
Douglas, S. (Contributor), Lowe, J. P. (Contributor), Mahon, M. F. (Contributor), Warren, J. (Contributor) & Whittlesey, M. K. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2006
DOI: 10.5517/cc8qnf1, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc8qnf1&sid=DataCite
Dataset

Cite this

@article{99f75c6185a84422bd92427e8d5e8364,

title = "Synthesis and structural characterisation of rhodium hydride complexes bearing N-heterocyclic carbene ligands",

abstract = "Addition of excesses of N-heterocyclic carbenes (NHCs) IEt 2Me2, IiPr2Me2 or ICy (IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene; IiPr2Me2 = 1,3-diisopropyl-4,5- dimethylimidazol-2-ylidene; ICy = 1,3-dicyclohexylimidazol-2-ylidene) to [HRh(PPh3)4] (1) affords an isomeric mixture of [HRh(NHC)(PPh3)2] (NHC = IEt2Me2 (cis-/trans-2), IiPr2Me2 (cis-/trans-3), ICy (cis-/trans-4) and [HRh(NHC)2(PPh3)] (IEt 2Me2(cis-/trans-5), IiPr2Me 2 (cis-/trans-6), ICy (cis-/trans-7)). Thermolysis of 1 with the aryl substituted NHC, 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene (IMesH 2), affords the bridging hydrido phosphido dimer, [{(PPh 3)2Rh}2(μ-H)(μ-PPh2)] (8), which is also the reaction product formed in the absence of carbene. When the rhodium precursor was changed from 1 to [HRh(CO)(PPh3)3] (9) and treated with either IMes (=1,3-dimesitylimidazol-2-ylidene) or ICy, the bis-NHC complexes trans-[HRh(CO)(IMes)2] (10) and trans-[HRh(CO)(ICy)2] (11) were formed. In contrast, the reaction of 9 with IiPr2Me2 gave [HRh(CO)(I iPr2Me2)2] (cis-/trans-12) and the unusual unsymmetrical dimer, [(PPh3)2Rh(μ-CO) 2Rh(IiPr2Me2)2] (13). The complexes trans-3, 8, 10 and 13 have been structurally characterised. {\textcopyright} 2005 Elsevier B.V. All rights reserved.",

keywords = "Hydride ligands, N-heterocyclic carbenes, Rhodium complexes",

author = "Susie Douglas and Lowe, {John P.} and Mahon, {Mary F.} and Warren, {John E.} and Whittlesey, {Michael K.}",

note = "23",

year = "2005",

month = nov,

day = "15",

doi = "10.1016/j.jorganchem.2005.02.017",

language = "English",

volume = "690",

pages = "5027--5035",

journal = "Journal of Organometallic Chemistry",

publisher = "Elsevier BV",

number = "23",

}

TY - JOUR

T1 - Synthesis and structural characterisation of rhodium hydride complexes bearing N-heterocyclic carbene ligands

AU - Douglas, Susie

AU - Lowe, John P.

AU - Mahon, Mary F.

AU - Warren, John E.

AU - Whittlesey, Michael K.

N1 - 23

PY - 2005/11/15

Y1 - 2005/11/15

N2 - Addition of excesses of N-heterocyclic carbenes (NHCs) IEt 2Me2, IiPr2Me2 or ICy (IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene; IiPr2Me2 = 1,3-diisopropyl-4,5- dimethylimidazol-2-ylidene; ICy = 1,3-dicyclohexylimidazol-2-ylidene) to [HRh(PPh3)4] (1) affords an isomeric mixture of [HRh(NHC)(PPh3)2] (NHC = IEt2Me2 (cis-/trans-2), IiPr2Me2 (cis-/trans-3), ICy (cis-/trans-4) and [HRh(NHC)2(PPh3)] (IEt 2Me2(cis-/trans-5), IiPr2Me 2 (cis-/trans-6), ICy (cis-/trans-7)). Thermolysis of 1 with the aryl substituted NHC, 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene (IMesH 2), affords the bridging hydrido phosphido dimer, [{(PPh 3)2Rh}2(μ-H)(μ-PPh2)] (8), which is also the reaction product formed in the absence of carbene. When the rhodium precursor was changed from 1 to [HRh(CO)(PPh3)3] (9) and treated with either IMes (=1,3-dimesitylimidazol-2-ylidene) or ICy, the bis-NHC complexes trans-[HRh(CO)(IMes)2] (10) and trans-[HRh(CO)(ICy)2] (11) were formed. In contrast, the reaction of 9 with IiPr2Me2 gave [HRh(CO)(I iPr2Me2)2] (cis-/trans-12) and the unusual unsymmetrical dimer, [(PPh3)2Rh(μ-CO) 2Rh(IiPr2Me2)2] (13). The complexes trans-3, 8, 10 and 13 have been structurally characterised. © 2005 Elsevier B.V. All rights reserved.

AB - Addition of excesses of N-heterocyclic carbenes (NHCs) IEt 2Me2, IiPr2Me2 or ICy (IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene; IiPr2Me2 = 1,3-diisopropyl-4,5- dimethylimidazol-2-ylidene; ICy = 1,3-dicyclohexylimidazol-2-ylidene) to [HRh(PPh3)4] (1) affords an isomeric mixture of [HRh(NHC)(PPh3)2] (NHC = IEt2Me2 (cis-/trans-2), IiPr2Me2 (cis-/trans-3), ICy (cis-/trans-4) and [HRh(NHC)2(PPh3)] (IEt 2Me2(cis-/trans-5), IiPr2Me 2 (cis-/trans-6), ICy (cis-/trans-7)). Thermolysis of 1 with the aryl substituted NHC, 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene (IMesH 2), affords the bridging hydrido phosphido dimer, [{(PPh 3)2Rh}2(μ-H)(μ-PPh2)] (8), which is also the reaction product formed in the absence of carbene. When the rhodium precursor was changed from 1 to [HRh(CO)(PPh3)3] (9) and treated with either IMes (=1,3-dimesitylimidazol-2-ylidene) or ICy, the bis-NHC complexes trans-[HRh(CO)(IMes)2] (10) and trans-[HRh(CO)(ICy)2] (11) were formed. In contrast, the reaction of 9 with IiPr2Me2 gave [HRh(CO)(I iPr2Me2)2] (cis-/trans-12) and the unusual unsymmetrical dimer, [(PPh3)2Rh(μ-CO) 2Rh(IiPr2Me2)2] (13). The complexes trans-3, 8, 10 and 13 have been structurally characterised. © 2005 Elsevier B.V. All rights reserved.

KW - Hydride ligands

KW - N-heterocyclic carbenes

KW - Rhodium complexes

U2 - 10.1016/j.jorganchem.2005.02.017

DO - 10.1016/j.jorganchem.2005.02.017

M3 - Article

VL - 690

SP - 5027

EP - 5035

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 23

ER -

Synthesis and structural characterisation of rhodium hydride complexes bearing N-heterocyclic carbene ligands

Abstract

Keywords

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Datasets

CCDC 260102: Experimental Crystal Structure Determination

CCDC 260100: Experimental Crystal Structure Determination

CCDC 260103: Experimental Crystal Structure Determination

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