N-Heterocyclic Carbene Stabilized trans-Dihydrido Aqua and Ethanol Complexes of Ruthenium: Precursors to Complexes with Ru-Heteroatom Bonds

Rodolphe F R Jazzar, Purvi H Bhatia, Mary F Mahon, Michael K Whittlesey

Research output: Contribution to journalArticle

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Abstract

Attempts to isolate the bis-N-heterocyclic carbene complex Ru(AsPh3)(IMes)2(CO)H2 (IMes = bis(1,3-(2,4,6-trimethylphenyl)imidazol-2-ylidene)) by crystn. with either ethanol or hexane yields instead the ethanol and water complexes Ru(IMes)2(CO)(EtOH)H2 (1) and Ru(IMes)2(CO)(H2O)H2 (2), resp. Both multinuclear NMR spectroscopy and x-ray crystallog. demonstrate that these two compds. are isostructural with a trans arrangement of the hydride ligands. Thermolysis of 1 results in decarbonylation of the bound ethanol ligand to yield Ru(IMes)2(CO)2H2 (3). Substitution of the coordinated solvent ligands in 1 or 2 occurs readily with p-ethoxyphenol to give Ru(IMes)2(CO)(HOC6H4-p-OEt)H2 (4), while treatment of 2 with 1-propanethiol affords the thiol complex Ru(IMes)2(CO)(HSCH2CH2CH3)H2 (8). Reaction of 8 with CO gives the thiolate hydride species Ru(IMes)2(CO)2(SCH2CH2CH3)H (9), whereas addn. of CO to either 1 or 2 affords Ru(IMes)2(CO)3 (5). The hydroxy hydride complex Ru(IMes)2(CO)2(OH)H (6) has been isolated as an intermediate on the pathway from 2 to 5. Addn. of CO2 or p-HO2CC5H4N to solns. of 2 yields the bicarbonate complex Ru(IMes)2(CO)(k2-O2COH)H (10) and the isonicotinate species Ru(IMes)2(CO)(k2-O2CC5H4N)H (11), resp. Addn. of CO to 10 affords Ru(IMes)2(CO)2(h1-O2COH)H (7). Treatment of complex 2 with excess acetonitrile yields the N-imidoylimidato complex Ru(IMes)2(CO)(NH:C(CH3)N:C(CH3)O)H (12), which arises from the formal addn. of two mols. of acetonitrile in head-to-tail fashion across the RuO-H bond. Compds. 1, 2, 6, 7, 8, 9, 11, and 12 have been structurally characterized by single-crystal x-ray diffraction.
LanguageEnglish
Pages670-683
Number of pages14
JournalOrganometallics
Volume22
Issue number4
StatusPublished - 2003

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Ruthenium
carbenes
Carbon Monoxide
ruthenium
hydrides
ethyl alcohol
Ethanol
ligands
acetonitrile
imidazoles
thiols
carbonates
x ray diffraction
substitutes
nuclear magnetic resonance
single crystals
Hydrides
water
spectroscopy
carbene

Keywords

  • PREP (Preparation)
  • ethanol
  • Crystal structure
  • RACT (Reactant or reagent) (prepn. and structures of nitrogen heterocyclic carbene stabilized trans-dihydrido aqua and ethanol complexes of ruthen
  • nitrogen heterocyclic carbene stabilized trans dihydrido aqua ethanol ruthenium
  • Molecular structure (of nitrogen heterocyclic carbene stabilized trans-dihydrido aqua
  • PRP (Properties)
  • Carbene complexes Role
  • and related complexes of ruthenium)
  • crystal mol structure nitrogen heterocyclic carbene stabilized ruthenium complex
  • SPN (Synthetic preparation)
  • RCT (Reactant)

Cite this

N-Heterocyclic Carbene Stabilized trans-Dihydrido Aqua and Ethanol Complexes of Ruthenium: Precursors to Complexes with Ru-Heteroatom Bonds. / Jazzar, Rodolphe F R; Bhatia, Purvi H; Mahon, Mary F; Whittlesey, Michael K.

In: Organometallics, Vol. 22, No. 4, 2003, p. 670-683.

Research output: Contribution to journalArticle

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title = "N-Heterocyclic Carbene Stabilized trans-Dihydrido Aqua and Ethanol Complexes of Ruthenium: Precursors to Complexes with Ru-Heteroatom Bonds",
abstract = "Attempts to isolate the bis-N-heterocyclic carbene complex Ru(AsPh3)(IMes)2(CO)H2 (IMes = bis(1,3-(2,4,6-trimethylphenyl)imidazol-2-ylidene)) by crystn. with either ethanol or hexane yields instead the ethanol and water complexes Ru(IMes)2(CO)(EtOH)H2 (1) and Ru(IMes)2(CO)(H2O)H2 (2), resp. Both multinuclear NMR spectroscopy and x-ray crystallog. demonstrate that these two compds. are isostructural with a trans arrangement of the hydride ligands. Thermolysis of 1 results in decarbonylation of the bound ethanol ligand to yield Ru(IMes)2(CO)2H2 (3). Substitution of the coordinated solvent ligands in 1 or 2 occurs readily with p-ethoxyphenol to give Ru(IMes)2(CO)(HOC6H4-p-OEt)H2 (4), while treatment of 2 with 1-propanethiol affords the thiol complex Ru(IMes)2(CO)(HSCH2CH2CH3)H2 (8). Reaction of 8 with CO gives the thiolate hydride species Ru(IMes)2(CO)2(SCH2CH2CH3)H (9), whereas addn. of CO to either 1 or 2 affords Ru(IMes)2(CO)3 (5). The hydroxy hydride complex Ru(IMes)2(CO)2(OH)H (6) has been isolated as an intermediate on the pathway from 2 to 5. Addn. of CO2 or p-HO2CC5H4N to solns. of 2 yields the bicarbonate complex Ru(IMes)2(CO)(k2-O2COH)H (10) and the isonicotinate species Ru(IMes)2(CO)(k2-O2CC5H4N)H (11), resp. Addn. of CO to 10 affords Ru(IMes)2(CO)2(h1-O2COH)H (7). Treatment of complex 2 with excess acetonitrile yields the N-imidoylimidato complex Ru(IMes)2(CO)(NH:C(CH3)N:C(CH3)O)H (12), which arises from the formal addn. of two mols. of acetonitrile in head-to-tail fashion across the RuO-H bond. Compds. 1, 2, 6, 7, 8, 9, 11, and 12 have been structurally characterized by single-crystal x-ray diffraction.",
keywords = "PREP (Preparation), ethanol, Crystal structure, RACT (Reactant or reagent) (prepn. and structures of nitrogen heterocyclic carbene stabilized trans-dihydrido aqua and ethanol complexes of ruthen, nitrogen heterocyclic carbene stabilized trans dihydrido aqua ethanol ruthenium, Molecular structure (of nitrogen heterocyclic carbene stabilized trans-dihydrido aqua, PRP (Properties), Carbene complexes Role, and related complexes of ruthenium), crystal mol structure nitrogen heterocyclic carbene stabilized ruthenium complex, SPN (Synthetic preparation), RCT (Reactant)",
author = "Jazzar, {Rodolphe F R} and Bhatia, {Purvi H} and Mahon, {Mary F} and Whittlesey, {Michael K}",
year = "2003",
language = "English",
volume = "22",
pages = "670--683",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "4",

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TY - JOUR

T1 - N-Heterocyclic Carbene Stabilized trans-Dihydrido Aqua and Ethanol Complexes of Ruthenium: Precursors to Complexes with Ru-Heteroatom Bonds

AU - Jazzar,Rodolphe F R

AU - Bhatia,Purvi H

AU - Mahon,Mary F

AU - Whittlesey,Michael K

PY - 2003

Y1 - 2003

N2 - Attempts to isolate the bis-N-heterocyclic carbene complex Ru(AsPh3)(IMes)2(CO)H2 (IMes = bis(1,3-(2,4,6-trimethylphenyl)imidazol-2-ylidene)) by crystn. with either ethanol or hexane yields instead the ethanol and water complexes Ru(IMes)2(CO)(EtOH)H2 (1) and Ru(IMes)2(CO)(H2O)H2 (2), resp. Both multinuclear NMR spectroscopy and x-ray crystallog. demonstrate that these two compds. are isostructural with a trans arrangement of the hydride ligands. Thermolysis of 1 results in decarbonylation of the bound ethanol ligand to yield Ru(IMes)2(CO)2H2 (3). Substitution of the coordinated solvent ligands in 1 or 2 occurs readily with p-ethoxyphenol to give Ru(IMes)2(CO)(HOC6H4-p-OEt)H2 (4), while treatment of 2 with 1-propanethiol affords the thiol complex Ru(IMes)2(CO)(HSCH2CH2CH3)H2 (8). Reaction of 8 with CO gives the thiolate hydride species Ru(IMes)2(CO)2(SCH2CH2CH3)H (9), whereas addn. of CO to either 1 or 2 affords Ru(IMes)2(CO)3 (5). The hydroxy hydride complex Ru(IMes)2(CO)2(OH)H (6) has been isolated as an intermediate on the pathway from 2 to 5. Addn. of CO2 or p-HO2CC5H4N to solns. of 2 yields the bicarbonate complex Ru(IMes)2(CO)(k2-O2COH)H (10) and the isonicotinate species Ru(IMes)2(CO)(k2-O2CC5H4N)H (11), resp. Addn. of CO to 10 affords Ru(IMes)2(CO)2(h1-O2COH)H (7). Treatment of complex 2 with excess acetonitrile yields the N-imidoylimidato complex Ru(IMes)2(CO)(NH:C(CH3)N:C(CH3)O)H (12), which arises from the formal addn. of two mols. of acetonitrile in head-to-tail fashion across the RuO-H bond. Compds. 1, 2, 6, 7, 8, 9, 11, and 12 have been structurally characterized by single-crystal x-ray diffraction.

AB - Attempts to isolate the bis-N-heterocyclic carbene complex Ru(AsPh3)(IMes)2(CO)H2 (IMes = bis(1,3-(2,4,6-trimethylphenyl)imidazol-2-ylidene)) by crystn. with either ethanol or hexane yields instead the ethanol and water complexes Ru(IMes)2(CO)(EtOH)H2 (1) and Ru(IMes)2(CO)(H2O)H2 (2), resp. Both multinuclear NMR spectroscopy and x-ray crystallog. demonstrate that these two compds. are isostructural with a trans arrangement of the hydride ligands. Thermolysis of 1 results in decarbonylation of the bound ethanol ligand to yield Ru(IMes)2(CO)2H2 (3). Substitution of the coordinated solvent ligands in 1 or 2 occurs readily with p-ethoxyphenol to give Ru(IMes)2(CO)(HOC6H4-p-OEt)H2 (4), while treatment of 2 with 1-propanethiol affords the thiol complex Ru(IMes)2(CO)(HSCH2CH2CH3)H2 (8). Reaction of 8 with CO gives the thiolate hydride species Ru(IMes)2(CO)2(SCH2CH2CH3)H (9), whereas addn. of CO to either 1 or 2 affords Ru(IMes)2(CO)3 (5). The hydroxy hydride complex Ru(IMes)2(CO)2(OH)H (6) has been isolated as an intermediate on the pathway from 2 to 5. Addn. of CO2 or p-HO2CC5H4N to solns. of 2 yields the bicarbonate complex Ru(IMes)2(CO)(k2-O2COH)H (10) and the isonicotinate species Ru(IMes)2(CO)(k2-O2CC5H4N)H (11), resp. Addn. of CO to 10 affords Ru(IMes)2(CO)2(h1-O2COH)H (7). Treatment of complex 2 with excess acetonitrile yields the N-imidoylimidato complex Ru(IMes)2(CO)(NH:C(CH3)N:C(CH3)O)H (12), which arises from the formal addn. of two mols. of acetonitrile in head-to-tail fashion across the RuO-H bond. Compds. 1, 2, 6, 7, 8, 9, 11, and 12 have been structurally characterized by single-crystal x-ray diffraction.

KW - PREP (Preparation)

KW - ethanol

KW - Crystal structure

KW - RACT (Reactant or reagent) (prepn. and structures of nitrogen heterocyclic carbene stabilized trans-dihydrido aqua and ethanol complexes of ruthen

KW - nitrogen heterocyclic carbene stabilized trans dihydrido aqua ethanol ruthenium

KW - Molecular structure (of nitrogen heterocyclic carbene stabilized trans-dihydrido aqua

KW - PRP (Properties)

KW - Carbene complexes Role

KW - and related complexes of ruthenium)

KW - crystal mol structure nitrogen heterocyclic carbene stabilized ruthenium complex

KW - SPN (Synthetic preparation)

KW - RCT (Reactant)

M3 - Article

VL - 22

SP - 670

EP - 683

JO - Organometallics

T2 - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 4

ER -