PC(sp(3))P pincer carbonyl complexes of iridium(I), and iridium(III)

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PC(sp(3))P pincer carbonyl complexes of iridium(I), and iridium(III). / Jonasson, Klara; Polukeev, Alexey; Wendt, Ola.

In: RSC Advances, Vol. 5, No. 20, 2015, p. 15534-15538.

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Jonasson, Klara ; Polukeev, Alexey ; Wendt, Ola. / PC(sp(3))P pincer carbonyl complexes of iridium(I), and iridium(III). In: RSC Advances. 2015 ; Vol. 5, No. 20. pp. 15534-15538.

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TY - JOUR

T1 - PC(sp(3))P pincer carbonyl complexes of iridium(I), and iridium(III)

AU - Jonasson, Klara

AU - Polukeev, Alexey

AU - Wendt, Ola

PY - 2015

Y1 - 2015

N2 - The previously reported complex trans-[IrHCl{cis-1,3-bis-(di-tert-butylphosphino)methyl} cyclohexane] (2) forms the 18-electron carbonyl compound anti-[Ir(CO)HCl{cis-1,3-bis-((di-tert-butylphosphino)methyl)} cyclohexane] (5a)upon reaction with 1 atm CO. The structural isomer syn-[IrH(CO)Cl{cis-1,3-bis-((di-tert- butylphosphino)methyl)}cyclohexane] (5b)is obtained directly upon complexation of the ligand (1) with IrCl3 center dot H2O in refluxing DMF syn-5b is the first iridium aliphatic pincer complex with this orientation of the hydrogens and is the thermodynamically more stable isomer. Both compounds 5a and 5b afford the Ir(I)complex trans-[Ir(CO){cis-1,3-bis-((di-tert-butylphosphino)methyl)}cyclohexane] (4)upon treatment with KO'Bu. Complex 4 was also synthesised in a more straightforward fashion from the previously known terminal nitrogen complex trans-[Ir(N-2){cis-1,3-bis-((di-tert-butylphosphino)-methyl)} cyclohexane] (3)under atmospheric CO. The complexes 4, 5a and 5b were characterised spectroscopically and in the solid state. IR data point to a more electron rich metal centre as compared to the corresponding aromatic complexes.

AB - The previously reported complex trans-[IrHCl{cis-1,3-bis-(di-tert-butylphosphino)methyl} cyclohexane] (2) forms the 18-electron carbonyl compound anti-[Ir(CO)HCl{cis-1,3-bis-((di-tert-butylphosphino)methyl)} cyclohexane] (5a)upon reaction with 1 atm CO. The structural isomer syn-[IrH(CO)Cl{cis-1,3-bis-((di-tert- butylphosphino)methyl)}cyclohexane] (5b)is obtained directly upon complexation of the ligand (1) with IrCl3 center dot H2O in refluxing DMF syn-5b is the first iridium aliphatic pincer complex with this orientation of the hydrogens and is the thermodynamically more stable isomer. Both compounds 5a and 5b afford the Ir(I)complex trans-[Ir(CO){cis-1,3-bis-((di-tert-butylphosphino)methyl)}cyclohexane] (4)upon treatment with KO'Bu. Complex 4 was also synthesised in a more straightforward fashion from the previously known terminal nitrogen complex trans-[Ir(N-2){cis-1,3-bis-((di-tert-butylphosphino)-methyl)} cyclohexane] (3)under atmospheric CO. The complexes 4, 5a and 5b were characterised spectroscopically and in the solid state. IR data point to a more electron rich metal centre as compared to the corresponding aromatic complexes.

U2 - 10.1039/c4ra15562a

DO - 10.1039/c4ra15562a

M3 - Article

VL - 5

SP - 15534

EP - 15538

JO - RSC Advances

T2 - RSC Advances

JF - RSC Advances

SN - 2046-2069

IS - 20

ER -