Diastereoselective synthesis of chiral octahedral iridium(III) phosphano-oxazoline complexes

Daniel Carmona; Joaquina Ferrer; Néstor García; Paola Ramírez; Fernando J. Lahoz; Pilar García-Orduña; Luis A. Oro

doi:10.1021/om301088x

Diastereoselective synthesis of chiral octahedral iridium(III) phosphano-oxazoline complexes

Daniel Carmona^*
, Joaquina Ferrer
, Néstor García
, Paola Ramírez
, Fernando J. Lahoz
, Pilar García-Orduña
, Luis A. Oro

^*Corresponding author for this work

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

2 Scopus citations

Abstract

Reaction of the dimer [Ir(μ-Cl)(η²-coe)₂] ₂ (coe = cyclooctene) with chiral phosphano-oxazoline ligands (PN*) renders neutral mononuclear iridium(I) complexes of the formula [IrCl(η²-coe)(PN*)] (1, 2), which in turn are oxidized to the corresponding iridium(III) hydride species [IrCl₂H(η ²-coe)(PN*)] (3, 4) by treatment with aqueous HCl. The latter react with diphosphanes (PP) in the presence of NaSbF₆ to afford cationic complexes of stoichiometry [IrClH(PN*)(PP)][SbF₆] (5-16). The fluorophenyldiphosphane-containing compounds [IrClH(PN*) (dfppe)][SbF₆] (15, 16) evolve to the corresponding Ir(I) species [Ir(PN*)(dfppe)][SbF₆] (17, 18) by HCl loss. The new compounds have been fully characterized by analytical and spectroscopic means, including the molecular structure determination of [IrCl₂H(η²- coe)(PNInd)] (3), [IrClH(PNInd)(dppen)][SbF₆] (6a,b), [IrClH(PNInd)(dppp)][SbF₆] (7a), [IrClH(PNiPr)(dppp)][SbF ₆] (13a), [IrClH(PNInd)(dfppe)][SbF₆] (15), [Ir(PNInd)(dfppe)][SbF₆] (17), and [Ir(PNiPr)(dfppe)][SbF ₆] (18) by X-ray diffractometric methods.

Original language	English
Pages (from-to)	1595-1608
Number of pages	14
Journal	Organometallics
Volume	32
Issue number	6
DOIs	https://doi.org/10.1021/om301088x
State	Published - 25 Mar 2013
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om301088x

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@article{c4e5827556b7473fa29050171aa17a63,

title = "Diastereoselective synthesis of chiral octahedral iridium(III) phosphano-oxazoline complexes",

abstract = "Reaction of the dimer [Ir(μ-Cl)(η2-coe)2] 2 (coe = cyclooctene) with chiral phosphano-oxazoline ligands (PN*) renders neutral mononuclear iridium(I) complexes of the formula [IrCl(η2-coe)(PN*)] (1, 2), which in turn are oxidized to the corresponding iridium(III) hydride species [IrCl2H(η 2-coe)(PN*)] (3, 4) by treatment with aqueous HCl. The latter react with diphosphanes (PP) in the presence of NaSbF6 to afford cationic complexes of stoichiometry [IrClH(PN*)(PP)][SbF6] (5-16). The fluorophenyldiphosphane-containing compounds [IrClH(PN*) (dfppe)][SbF6] (15, 16) evolve to the corresponding Ir(I) species [Ir(PN*)(dfppe)][SbF6] (17, 18) by HCl loss. The new compounds have been fully characterized by analytical and spectroscopic means, including the molecular structure determination of [IrCl2H(η2- coe)(PNInd)] (3), [IrClH(PNInd)(dppen)][SbF6] (6a,b), [IrClH(PNInd)(dppp)][SbF6] (7a), [IrClH(PNiPr)(dppp)][SbF 6] (13a), [IrClH(PNInd)(dfppe)][SbF6] (15), [Ir(PNInd)(dfppe)][SbF6] (17), and [Ir(PNiPr)(dfppe)][SbF 6] (18) by X-ray diffractometric methods.",

author = "Daniel Carmona and Joaquina Ferrer and N{\'e}stor Garc{\'i}a and Paola Ram{\'i}rez and Lahoz, \{Fernando J.\} and Pilar Garc{\'i}a-Ordu{\~n}a and Oro, \{Luis A.\}",

year = "2013",

month = mar,

day = "25",

doi = "10.1021/om301088x",

language = "English",

volume = "32",

pages = "1595--1608",

journal = "Organometallics",

issn = "0276-7333",

number = "6",

}

TY - JOUR

T1 - Diastereoselective synthesis of chiral octahedral iridium(III) phosphano-oxazoline complexes

AU - Carmona, Daniel

AU - Ferrer, Joaquina

AU - García, Néstor

AU - Ramírez, Paola

AU - Lahoz, Fernando J.

AU - García-Orduña, Pilar

AU - Oro, Luis A.

PY - 2013/3/25

Y1 - 2013/3/25

N2 - Reaction of the dimer [Ir(μ-Cl)(η2-coe)2] 2 (coe = cyclooctene) with chiral phosphano-oxazoline ligands (PN*) renders neutral mononuclear iridium(I) complexes of the formula [IrCl(η2-coe)(PN*)] (1, 2), which in turn are oxidized to the corresponding iridium(III) hydride species [IrCl2H(η 2-coe)(PN*)] (3, 4) by treatment with aqueous HCl. The latter react with diphosphanes (PP) in the presence of NaSbF6 to afford cationic complexes of stoichiometry [IrClH(PN*)(PP)][SbF6] (5-16). The fluorophenyldiphosphane-containing compounds [IrClH(PN*) (dfppe)][SbF6] (15, 16) evolve to the corresponding Ir(I) species [Ir(PN*)(dfppe)][SbF6] (17, 18) by HCl loss. The new compounds have been fully characterized by analytical and spectroscopic means, including the molecular structure determination of [IrCl2H(η2- coe)(PNInd)] (3), [IrClH(PNInd)(dppen)][SbF6] (6a,b), [IrClH(PNInd)(dppp)][SbF6] (7a), [IrClH(PNiPr)(dppp)][SbF 6] (13a), [IrClH(PNInd)(dfppe)][SbF6] (15), [Ir(PNInd)(dfppe)][SbF6] (17), and [Ir(PNiPr)(dfppe)][SbF 6] (18) by X-ray diffractometric methods.

AB - Reaction of the dimer [Ir(μ-Cl)(η2-coe)2] 2 (coe = cyclooctene) with chiral phosphano-oxazoline ligands (PN*) renders neutral mononuclear iridium(I) complexes of the formula [IrCl(η2-coe)(PN*)] (1, 2), which in turn are oxidized to the corresponding iridium(III) hydride species [IrCl2H(η 2-coe)(PN*)] (3, 4) by treatment with aqueous HCl. The latter react with diphosphanes (PP) in the presence of NaSbF6 to afford cationic complexes of stoichiometry [IrClH(PN*)(PP)][SbF6] (5-16). The fluorophenyldiphosphane-containing compounds [IrClH(PN*) (dfppe)][SbF6] (15, 16) evolve to the corresponding Ir(I) species [Ir(PN*)(dfppe)][SbF6] (17, 18) by HCl loss. The new compounds have been fully characterized by analytical and spectroscopic means, including the molecular structure determination of [IrCl2H(η2- coe)(PNInd)] (3), [IrClH(PNInd)(dppen)][SbF6] (6a,b), [IrClH(PNInd)(dppp)][SbF6] (7a), [IrClH(PNiPr)(dppp)][SbF 6] (13a), [IrClH(PNInd)(dfppe)][SbF6] (15), [Ir(PNInd)(dfppe)][SbF6] (17), and [Ir(PNiPr)(dfppe)][SbF 6] (18) by X-ray diffractometric methods.

UR - https://www.scopus.com/pages/publications/84875458882

U2 - 10.1021/om301088x

DO - 10.1021/om301088x

M3 - Article

AN - SCOPUS:84875458882

SN - 0276-7333

VL - 32

SP - 1595

EP - 1608

JO - Organometallics

JF - Organometallics

IS - 6

ER -

Diastereoselective synthesis of chiral octahedral iridium(III) phosphano-oxazoline complexes

Abstract

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