Dihydrogen complexes of rhodium: [RhH2(H-2)(x)(PR3)(2)](+)(R = Cy, Pr-i; x = 1, 2)

M J Ingleson, S K Brayshaw, M F Mahon, G D Ruggiero, A S Weller

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Abstract

Addition of H-2 (4 atm at 298 K) to [Rh(nbd)(PR3)(2)][BAr4F] [R = Cy, Pr-i] affords Rh(III) dihydride/dihydrogen complexes. For R = Cy, complex la results, which has been shown by low-temperature NMR experiments to be the bisdihydrogen/bis-hydride complex [Rh(H)(2)(eta(2) -H-2)(2)(PCY3)(2)][BAr4F]. An X-ray diffraction study on la confirmed the {Rh(PCY3)(2)} core structure, but due to a poor data set, the hydrogen ligands were not located. DFT calculations at the B3LYP/DZVP level support the formulation as a Rh(III) dihydride/dihydrogen complex with cis hydride ligands. For R = Pr-i, the equivalent species, [Rh(H)(2) (eta(2) -H-2)(2)((PPr3)-Pr-i)(2)][BAr4F] 2a, is formed, along with another complex that was spectroscopically identified as the mono-dihydrogen, bis-hydride solvent complex [Rh(H)(2) (eta(2) - H-2) (CD2Cl2)((PPr3)-Pr-i)(2)] [BAr (F)(4)] 2b. The analogous complex with PCy3 ligands, [Rh(H)(2)(eta(2)-H-2)(CD2Cl2)(PCy3)(2)][BAr4F] 1b, can be observed by reducing the H-2 pressure to 2 atm (at 298 K). Under vacuum, the dihydrogen ligands are lost in these complexes to form the spectroscopically characterized species, tentatively identified as the bis hydrides [Rh(H)(2)(L)(2)(PR3)(2)][BAr (F)(4)] (1c R = Cy; 2c R = Pr-i; L = CD2Cl2 or agostic interaction). Exposure of 1c or 2c to a H2 atmosphere regenerates the dihydrogen/bis-hydride complexes, while adding acetonitrile affords the bis-hydride MeCN adduct complexes [Rh(H)(2)(NCMe)(2)(PR3)(2)][BAr4F]. The clihydrogen complexes lose [HPR3][BAr4F] at or just above ambient temperature, suggested to be by heterolytic splitting of coordinated H2, to ultimately afford the dicationic cluster compounds of the type [Rh-6(PR3)(6)(mu-H)(12)][BAr4F](2) in moderate yield.
Original languageEnglish
Pages (from-to)3162-3171
Number of pages10
JournalInorganic Chemistry
Volume44
Issue number9
DOIs
Publication statusPublished - 2005

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Rhodium
rhodium
Hydrides
hydrides
Ligands
dihydrides
Hydrogen
ligands
Discrete Fourier transforms
adducts
ambient temperature
acetonitrile
Nuclear magnetic resonance
Vacuum
formulations
atmospheres
X ray diffraction
Temperature
vacuum
nuclear magnetic resonance

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Dihydrogen complexes of rhodium: [RhH2(H-2)(x)(PR3)(2)](+)(R = Cy, Pr-i; x = 1, 2). / Ingleson, M J; Brayshaw, S K; Mahon, M F; Ruggiero, G D; Weller, A S.

In: Inorganic Chemistry, Vol. 44, No. 9, 2005, p. 3162-3171.

Research output: Contribution to journalArticle

Ingleson, MJ, Brayshaw, SK, Mahon, MF, Ruggiero, GD & Weller, AS 2005, 'Dihydrogen complexes of rhodium: [RhH2(H-2)(x)(PR3)(2)](+)(R = Cy, Pr-i; x = 1, 2)', Inorganic Chemistry, vol. 44, no. 9, pp. 3162-3171. https://doi.org/10.1021/ic0482739
Ingleson, M J ; Brayshaw, S K ; Mahon, M F ; Ruggiero, G D ; Weller, A S. / Dihydrogen complexes of rhodium: [RhH2(H-2)(x)(PR3)(2)](+)(R = Cy, Pr-i; x = 1, 2). In: Inorganic Chemistry. 2005 ; Vol. 44, No. 9. pp. 3162-3171.
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abstract = "Addition of H-2 (4 atm at 298 K) to [Rh(nbd)(PR3)(2)][BAr4F] [R = Cy, Pr-i] affords Rh(III) dihydride/dihydrogen complexes. For R = Cy, complex la results, which has been shown by low-temperature NMR experiments to be the bisdihydrogen/bis-hydride complex [Rh(H)(2)(eta(2) -H-2)(2)(PCY3)(2)][BAr4F]. An X-ray diffraction study on la confirmed the {Rh(PCY3)(2)} core structure, but due to a poor data set, the hydrogen ligands were not located. DFT calculations at the B3LYP/DZVP level support the formulation as a Rh(III) dihydride/dihydrogen complex with cis hydride ligands. For R = Pr-i, the equivalent species, [Rh(H)(2) (eta(2) -H-2)(2)((PPr3)-Pr-i)(2)][BAr4F] 2a, is formed, along with another complex that was spectroscopically identified as the mono-dihydrogen, bis-hydride solvent complex [Rh(H)(2) (eta(2) - H-2) (CD2Cl2)((PPr3)-Pr-i)(2)] [BAr (F)(4)] 2b. The analogous complex with PCy3 ligands, [Rh(H)(2)(eta(2)-H-2)(CD2Cl2)(PCy3)(2)][BAr4F] 1b, can be observed by reducing the H-2 pressure to 2 atm (at 298 K). Under vacuum, the dihydrogen ligands are lost in these complexes to form the spectroscopically characterized species, tentatively identified as the bis hydrides [Rh(H)(2)(L)(2)(PR3)(2)][BAr (F)(4)] (1c R = Cy; 2c R = Pr-i; L = CD2Cl2 or agostic interaction). Exposure of 1c or 2c to a H2 atmosphere regenerates the dihydrogen/bis-hydride complexes, while adding acetonitrile affords the bis-hydride MeCN adduct complexes [Rh(H)(2)(NCMe)(2)(PR3)(2)][BAr4F]. The clihydrogen complexes lose [HPR3][BAr4F] at or just above ambient temperature, suggested to be by heterolytic splitting of coordinated H2, to ultimately afford the dicationic cluster compounds of the type [Rh-6(PR3)(6)(mu-H)(12)][BAr4F](2) in moderate yield.",
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T1 - Dihydrogen complexes of rhodium: [RhH2(H-2)(x)(PR3)(2)](+)(R = Cy, Pr-i; x = 1, 2)

AU - Ingleson, M J

AU - Brayshaw, S K

AU - Mahon, M F

AU - Ruggiero, G D

AU - Weller, A S

N1 - ID number: ISI:000228813400029

PY - 2005

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N2 - Addition of H-2 (4 atm at 298 K) to [Rh(nbd)(PR3)(2)][BAr4F] [R = Cy, Pr-i] affords Rh(III) dihydride/dihydrogen complexes. For R = Cy, complex la results, which has been shown by low-temperature NMR experiments to be the bisdihydrogen/bis-hydride complex [Rh(H)(2)(eta(2) -H-2)(2)(PCY3)(2)][BAr4F]. An X-ray diffraction study on la confirmed the {Rh(PCY3)(2)} core structure, but due to a poor data set, the hydrogen ligands were not located. DFT calculations at the B3LYP/DZVP level support the formulation as a Rh(III) dihydride/dihydrogen complex with cis hydride ligands. For R = Pr-i, the equivalent species, [Rh(H)(2) (eta(2) -H-2)(2)((PPr3)-Pr-i)(2)][BAr4F] 2a, is formed, along with another complex that was spectroscopically identified as the mono-dihydrogen, bis-hydride solvent complex [Rh(H)(2) (eta(2) - H-2) (CD2Cl2)((PPr3)-Pr-i)(2)] [BAr (F)(4)] 2b. The analogous complex with PCy3 ligands, [Rh(H)(2)(eta(2)-H-2)(CD2Cl2)(PCy3)(2)][BAr4F] 1b, can be observed by reducing the H-2 pressure to 2 atm (at 298 K). Under vacuum, the dihydrogen ligands are lost in these complexes to form the spectroscopically characterized species, tentatively identified as the bis hydrides [Rh(H)(2)(L)(2)(PR3)(2)][BAr (F)(4)] (1c R = Cy; 2c R = Pr-i; L = CD2Cl2 or agostic interaction). Exposure of 1c or 2c to a H2 atmosphere regenerates the dihydrogen/bis-hydride complexes, while adding acetonitrile affords the bis-hydride MeCN adduct complexes [Rh(H)(2)(NCMe)(2)(PR3)(2)][BAr4F]. The clihydrogen complexes lose [HPR3][BAr4F] at or just above ambient temperature, suggested to be by heterolytic splitting of coordinated H2, to ultimately afford the dicationic cluster compounds of the type [Rh-6(PR3)(6)(mu-H)(12)][BAr4F](2) in moderate yield.

AB - Addition of H-2 (4 atm at 298 K) to [Rh(nbd)(PR3)(2)][BAr4F] [R = Cy, Pr-i] affords Rh(III) dihydride/dihydrogen complexes. For R = Cy, complex la results, which has been shown by low-temperature NMR experiments to be the bisdihydrogen/bis-hydride complex [Rh(H)(2)(eta(2) -H-2)(2)(PCY3)(2)][BAr4F]. An X-ray diffraction study on la confirmed the {Rh(PCY3)(2)} core structure, but due to a poor data set, the hydrogen ligands were not located. DFT calculations at the B3LYP/DZVP level support the formulation as a Rh(III) dihydride/dihydrogen complex with cis hydride ligands. For R = Pr-i, the equivalent species, [Rh(H)(2) (eta(2) -H-2)(2)((PPr3)-Pr-i)(2)][BAr4F] 2a, is formed, along with another complex that was spectroscopically identified as the mono-dihydrogen, bis-hydride solvent complex [Rh(H)(2) (eta(2) - H-2) (CD2Cl2)((PPr3)-Pr-i)(2)] [BAr (F)(4)] 2b. The analogous complex with PCy3 ligands, [Rh(H)(2)(eta(2)-H-2)(CD2Cl2)(PCy3)(2)][BAr4F] 1b, can be observed by reducing the H-2 pressure to 2 atm (at 298 K). Under vacuum, the dihydrogen ligands are lost in these complexes to form the spectroscopically characterized species, tentatively identified as the bis hydrides [Rh(H)(2)(L)(2)(PR3)(2)][BAr (F)(4)] (1c R = Cy; 2c R = Pr-i; L = CD2Cl2 or agostic interaction). Exposure of 1c or 2c to a H2 atmosphere regenerates the dihydrogen/bis-hydride complexes, while adding acetonitrile affords the bis-hydride MeCN adduct complexes [Rh(H)(2)(NCMe)(2)(PR3)(2)][BAr4F]. The clihydrogen complexes lose [HPR3][BAr4F] at or just above ambient temperature, suggested to be by heterolytic splitting of coordinated H2, to ultimately afford the dicationic cluster compounds of the type [Rh-6(PR3)(6)(mu-H)(12)][BAr4F](2) in moderate yield.

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DO - 10.1021/ic0482739

M3 - Article

VL - 44

SP - 3162

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 9

ER -