Hemilabile and bimetallic coordination in Rh and Ir complexes of NCN pincer ligands

Giulia Mancano; Michael J. Page; Mohan Bhadbhade; Barbara A. Messerle

doi:10.1021/ic501158x

Hemilabile and bimetallic coordination in Rh and Ir complexes of NCN pincer ligands

Giulia Mancano, Michael J. Page, Mohan Bhadbhade, Barbara A. Messerle^*

^*Corresponding author for this work

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

49 Citations (Scopus)

Abstract

Two new pincer ligands have been developed that contain a central N-heterocyclic carbene (NHC) moiety linked to two pendant pyrazole groups by either a methylene (NCN^me) or ethylene (NCN^et) chain. The coordination of these two ligands to rhodium and iridium resulted in a variety of binding modes. Tridentate coordination of the ligands was observed in the complexes [Rh(NCN^me)(COD)]BPh₄ (8), [Ir(NCN^me)(COD)]BPh₄ (10), [Rh(NCN^et)(CO)₂]BPh₄ (13), and [Ir(NCN^me)(CO)₂]BPh₄ (14), and monodentate NHC coordination was observed for [Ir(NCN^me)₂(COD)]BPh₄ (11) and [Ir(NCN^et)₂(COD)]BPh₄ (12). Both tridentate and bidentate coordination modes were characterized for [Rh(NCN^et)(COD)]BPh₄ (9) in the solution and solid state, respectively, while an unusual bridging mode was observed for the bimetallic complex [Rh(μ-NCN^me)(CO)]₂(BPh₄)₂ (15). The impact of this diverse coordination chemistry on the efficiency of the complexes as catalysts for the addition of NH, OH, and SiH bonds to alkynes was explored.

Original language	English
Pages (from-to)	10159-10170
Number of pages	12
Journal	Inorganic Chemistry
Volume	53
Issue number	19
DOIs	https://doi.org/10.1021/ic501158x
Publication status	Published - 6 Oct 2014
Externally published	Yes

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10.1021/ic501158x

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title = "Hemilabile and bimetallic coordination in Rh and Ir complexes of NCN pincer ligands",

abstract = "Two new pincer ligands have been developed that contain a central N-heterocyclic carbene (NHC) moiety linked to two pendant pyrazole groups by either a methylene (NCNme) or ethylene (NCNet) chain. The coordination of these two ligands to rhodium and iridium resulted in a variety of binding modes. Tridentate coordination of the ligands was observed in the complexes [Rh(NCNme)(COD)]BPh4 (8), [Ir(NCNme)(COD)]BPh4 (10), [Rh(NCNet)(CO)2]BPh4 (13), and [Ir(NCNme)(CO)2]BPh4 (14), and monodentate NHC coordination was observed for [Ir(NCNme)2(COD)]BPh4 (11) and [Ir(NCNet)2(COD)]BPh4 (12). Both tridentate and bidentate coordination modes were characterized for [Rh(NCNet)(COD)]BPh4 (9) in the solution and solid state, respectively, while an unusual bridging mode was observed for the bimetallic complex [Rh(μ-NCNme)(CO)]2(BPh4)2 (15). The impact of this diverse coordination chemistry on the efficiency of the complexes as catalysts for the addition of NH, OH, and SiH bonds to alkynes was explored.",

author = "Giulia Mancano and Page, {Michael J.} and Mohan Bhadbhade and Messerle, {Barbara A.}",

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AU - Page, Michael J.

AU - Bhadbhade, Mohan

AU - Messerle, Barbara A.

PY - 2014/10/6

Y1 - 2014/10/6

N2 - Two new pincer ligands have been developed that contain a central N-heterocyclic carbene (NHC) moiety linked to two pendant pyrazole groups by either a methylene (NCNme) or ethylene (NCNet) chain. The coordination of these two ligands to rhodium and iridium resulted in a variety of binding modes. Tridentate coordination of the ligands was observed in the complexes [Rh(NCNme)(COD)]BPh4 (8), [Ir(NCNme)(COD)]BPh4 (10), [Rh(NCNet)(CO)2]BPh4 (13), and [Ir(NCNme)(CO)2]BPh4 (14), and monodentate NHC coordination was observed for [Ir(NCNme)2(COD)]BPh4 (11) and [Ir(NCNet)2(COD)]BPh4 (12). Both tridentate and bidentate coordination modes were characterized for [Rh(NCNet)(COD)]BPh4 (9) in the solution and solid state, respectively, while an unusual bridging mode was observed for the bimetallic complex [Rh(μ-NCNme)(CO)]2(BPh4)2 (15). The impact of this diverse coordination chemistry on the efficiency of the complexes as catalysts for the addition of NH, OH, and SiH bonds to alkynes was explored.

AB - Two new pincer ligands have been developed that contain a central N-heterocyclic carbene (NHC) moiety linked to two pendant pyrazole groups by either a methylene (NCNme) or ethylene (NCNet) chain. The coordination of these two ligands to rhodium and iridium resulted in a variety of binding modes. Tridentate coordination of the ligands was observed in the complexes [Rh(NCNme)(COD)]BPh4 (8), [Ir(NCNme)(COD)]BPh4 (10), [Rh(NCNet)(CO)2]BPh4 (13), and [Ir(NCNme)(CO)2]BPh4 (14), and monodentate NHC coordination was observed for [Ir(NCNme)2(COD)]BPh4 (11) and [Ir(NCNet)2(COD)]BPh4 (12). Both tridentate and bidentate coordination modes were characterized for [Rh(NCNet)(COD)]BPh4 (9) in the solution and solid state, respectively, while an unusual bridging mode was observed for the bimetallic complex [Rh(μ-NCNme)(CO)]2(BPh4)2 (15). The impact of this diverse coordination chemistry on the efficiency of the complexes as catalysts for the addition of NH, OH, and SiH bonds to alkynes was explored.

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JO - Inorganic Chemistry

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Hemilabile and bimetallic coordination in Rh and Ir complexes of NCN pincer ligands

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Boron and Silicon Based Pincer Ligands for Environmentally Responsible Catalysis

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Hemilabile and bimetallic coordination in Rh and Ir complexes of NCN pincer ligands

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Boron and Silicon Based Pincer Ligands for Environmentally Responsible Catalysis

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