Structure and dynamic NMR behavior of rhodium complexes supported by Lewis acidic group 13 metallatranes

James T. Moore, Nicholas E. Smith, Connie C. Lu

Research output: Contribution to journalArticle

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Abstract

Monovalent Rh was installed into the group 13 metallatranes, M[N(o-(NCH2P(iPr)2)C6H4)3] (where M = Al and Ga, abbreviated as ML) to generate Rh → M bonds in the parent complexes, Cl-RhAlL (1-Cl) and Cl-RhGaL (2-Cl). The electron-withdrawing nature of the group 13 metalloids was probed by cyclic voltammetry, and Rh-Ga was found to be more electron-deficient than Rh-Al (Epc = -2.07 and -1.95 V vs. Fc+/Fc for 1-Cl and 2-Cl, respectively). Both 1-Cl and 2-Cl were further functionalized through metathesis reactions using MeLi to generate 1-CH3 and 2-CH3, respectively, or using LiHBEt3 to form 1-H and 2-H, respectively. The solid-state structures of all Rh-M bimetallics feature Rh-M bond lengths that are less than the sum of the covalent radii of Rh and M (Rh-M: 2.50-2.54 Å for 1-X and 2.49-2.46 Å for 2-X, where X = Cl, CH3, and H). In the Rh-M structures, the Rh center is distorted from square pyramidal geometry due to steric interactions between X and the isopropyl substituents of L. Finally, all the Rh-M bimetallics exhibit fluxionality that involves phosphine exchange. Of note, the two phosphines cis to the X ligand become inequivalent at low temperature. The activation barrier to exchange these two phosphine donors is: 14.9, 14.2, 10.9, and 11.5 kcal mol-1 for 1-Cl, 2-Cl, 1-H, and 2-H, respectively. The activation barriers for 1-CH3 and 2-CH3 are both >15.2 kcal mol-1. At high temperature, 2-Cl was also found to exchange all three phosphine donors. Mechanisms for the different types of phosphine exchange are proposed.

Original languageEnglish (US)
Pages (from-to)5689-5701
Number of pages13
JournalDalton Transactions
Volume46
Issue number17
DOIs
StatePublished - Jan 1 2017

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phosphine
Rhodium
Nuclear magnetic resonance
Chemical activation
Metalloids
Phosphines
Electrons
Bond length
Cyclic voltammetry
Ion exchange
Ligands
Temperature
Geometry

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Structure and dynamic NMR behavior of rhodium complexes supported by Lewis acidic group 13 metallatranes. / Moore, James T.; Smith, Nicholas E.; Lu, Connie C.

In: Dalton Transactions, Vol. 46, No. 17, 01.01.2017, p. 5689-5701.

Research output: Contribution to journalArticle

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title = "Structure and dynamic NMR behavior of rhodium complexes supported by Lewis acidic group 13 metallatranes",
abstract = "Monovalent Rh was installed into the group 13 metallatranes, M[N(o-(NCH2P(iPr)2)C6H4)3] (where M = Al and Ga, abbreviated as ML) to generate Rh → M bonds in the parent complexes, Cl-RhAlL (1-Cl) and Cl-RhGaL (2-Cl). The electron-withdrawing nature of the group 13 metalloids was probed by cyclic voltammetry, and Rh-Ga was found to be more electron-deficient than Rh-Al (Epc = -2.07 and -1.95 V vs. Fc+/Fc for 1-Cl and 2-Cl, respectively). Both 1-Cl and 2-Cl were further functionalized through metathesis reactions using MeLi to generate 1-CH3 and 2-CH3, respectively, or using LiHBEt3 to form 1-H and 2-H, respectively. The solid-state structures of all Rh-M bimetallics feature Rh-M bond lengths that are less than the sum of the covalent radii of Rh and M (Rh-M: 2.50-2.54 {\AA} for 1-X and 2.49-2.46 {\AA} for 2-X, where X = Cl, CH3, and H). In the Rh-M structures, the Rh center is distorted from square pyramidal geometry due to steric interactions between X and the isopropyl substituents of L. Finally, all the Rh-M bimetallics exhibit fluxionality that involves phosphine exchange. Of note, the two phosphines cis to the X ligand become inequivalent at low temperature. The activation barrier to exchange these two phosphine donors is: 14.9, 14.2, 10.9, and 11.5 kcal mol-1 for 1-Cl, 2-Cl, 1-H, and 2-H, respectively. The activation barriers for 1-CH3 and 2-CH3 are both >15.2 kcal mol-1. At high temperature, 2-Cl was also found to exchange all three phosphine donors. Mechanisms for the different types of phosphine exchange are proposed.",
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N2 - Monovalent Rh was installed into the group 13 metallatranes, M[N(o-(NCH2P(iPr)2)C6H4)3] (where M = Al and Ga, abbreviated as ML) to generate Rh → M bonds in the parent complexes, Cl-RhAlL (1-Cl) and Cl-RhGaL (2-Cl). The electron-withdrawing nature of the group 13 metalloids was probed by cyclic voltammetry, and Rh-Ga was found to be more electron-deficient than Rh-Al (Epc = -2.07 and -1.95 V vs. Fc+/Fc for 1-Cl and 2-Cl, respectively). Both 1-Cl and 2-Cl were further functionalized through metathesis reactions using MeLi to generate 1-CH3 and 2-CH3, respectively, or using LiHBEt3 to form 1-H and 2-H, respectively. The solid-state structures of all Rh-M bimetallics feature Rh-M bond lengths that are less than the sum of the covalent radii of Rh and M (Rh-M: 2.50-2.54 Å for 1-X and 2.49-2.46 Å for 2-X, where X = Cl, CH3, and H). In the Rh-M structures, the Rh center is distorted from square pyramidal geometry due to steric interactions between X and the isopropyl substituents of L. Finally, all the Rh-M bimetallics exhibit fluxionality that involves phosphine exchange. Of note, the two phosphines cis to the X ligand become inequivalent at low temperature. The activation barrier to exchange these two phosphine donors is: 14.9, 14.2, 10.9, and 11.5 kcal mol-1 for 1-Cl, 2-Cl, 1-H, and 2-H, respectively. The activation barriers for 1-CH3 and 2-CH3 are both >15.2 kcal mol-1. At high temperature, 2-Cl was also found to exchange all three phosphine donors. Mechanisms for the different types of phosphine exchange are proposed.

AB - Monovalent Rh was installed into the group 13 metallatranes, M[N(o-(NCH2P(iPr)2)C6H4)3] (where M = Al and Ga, abbreviated as ML) to generate Rh → M bonds in the parent complexes, Cl-RhAlL (1-Cl) and Cl-RhGaL (2-Cl). The electron-withdrawing nature of the group 13 metalloids was probed by cyclic voltammetry, and Rh-Ga was found to be more electron-deficient than Rh-Al (Epc = -2.07 and -1.95 V vs. Fc+/Fc for 1-Cl and 2-Cl, respectively). Both 1-Cl and 2-Cl were further functionalized through metathesis reactions using MeLi to generate 1-CH3 and 2-CH3, respectively, or using LiHBEt3 to form 1-H and 2-H, respectively. The solid-state structures of all Rh-M bimetallics feature Rh-M bond lengths that are less than the sum of the covalent radii of Rh and M (Rh-M: 2.50-2.54 Å for 1-X and 2.49-2.46 Å for 2-X, where X = Cl, CH3, and H). In the Rh-M structures, the Rh center is distorted from square pyramidal geometry due to steric interactions between X and the isopropyl substituents of L. Finally, all the Rh-M bimetallics exhibit fluxionality that involves phosphine exchange. Of note, the two phosphines cis to the X ligand become inequivalent at low temperature. The activation barrier to exchange these two phosphine donors is: 14.9, 14.2, 10.9, and 11.5 kcal mol-1 for 1-Cl, 2-Cl, 1-H, and 2-H, respectively. The activation barriers for 1-CH3 and 2-CH3 are both >15.2 kcal mol-1. At high temperature, 2-Cl was also found to exchange all three phosphine donors. Mechanisms for the different types of phosphine exchange are proposed.

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