A Stable Coordination Complex of Rh(IV) in an N,O-Donor Environment

Sinha, Shashi B.; Shopov, Dimitar Y.; Sharninghausen, Liam S.; Vinyard, David J.; Mercado, Brandon Q.; Brudvig, Gary W.; Crabtree, Robert H.

doi:10.1021/jacs.5b12148

A Stable Coordination Complex of Rh(IV) in an N,O-Donor Environment

Journal Article · Sun Dec 06 23:00:00 EST 2015 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.5b12148· OSTI ID:1387523

Sinha, Shashi B. ^[1]; Shopov, Dimitar Y. ^[1]; Sharninghausen, Liam S. ^[1]; Vinyard, David J. ^[1]; Mercado, Brandon Q. ^[1]; Brudvig, Gary W. ^[1]; Crabtree, Robert H. ^[1]

Yale Univ., New Haven, CT (United States)

Herein we describe facial and meridional isomers of [Rh^III(pyalk)₃], as well as meridional [Rh^IV(pyalk)₃]⁺ {pyalk =2-(2-pyridyl)-2-propanoate}, the first coordination complex in an N,O-donor environment to show a clean, reversible Rh^III/IV redox couple and to have a stable Rh(IV) form, which we characterize by EPR and UV–visible spectroscopy as well as X-ray crystallography. The unprecedented stability of the Rh(IV) species is ascribed to the exceptional donor strength of the ligands, their oxidation resistance, and the meridional coordination geometry.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0001059; FG02-07ER15909

OSTI ID:: 1387523

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 50 Vol. 137; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (36)

Experimental and Theoretical Investigations of the Existence of Cu II , Cu III , and Cu IV in Copper Corrolato Complexes Sinha, Woormileela; Sommer, Michael G.; Deibel, Naina Angewandte Chemie International Edition, Vol. 54, Issue 46 https://doi.org/10.1002/anie.201507330	journal	September 2015
�ber Neue Hexafluororhodate(IV): AIIRhIVF6 (AII = Ba, Sr, Ca, Mg, Zn, Cd, Hg, Ni sowie Cu) Wilhelm, V.; Hoppe, R. Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 407, Issue 1 https://doi.org/10.1002/zaac.19744070103	journal	July 1974
The chemistry of ruthenium, osmium, rhodium, iridium, palladium and platinum in the higher oxidation states Gulliver, D. J.; Levason, W. Coordination Chemistry Reviews, Vol. 46 https://doi.org/10.1016/0010-8545(82)85001-7	journal	October 1982
Formation and stability of the platinum and rhodium oxides at high oxygen pressures and the structures of Pt3O4, β-PtO2 and RhO2 Muller, Olaf; Roy, Rustum Journal of the Less Common Metals, Vol. 16, Issue 2 https://doi.org/10.1016/0022-5088(68)90070-2	journal	October 1968
Synthesis and properties of two new members of the rutile family RhO2 and PtO2 Shannon, R. D. Solid State Communications, Vol. 6, Issue 3 https://doi.org/10.1016/0038-1098(68)90019-7	journal	March 1968
Bildung und thermische stabilität von rhodium-oxiden Bayer, G.; Wiedemann, H. G. Thermochimica Acta, Vol. 15, Issue 2 https://doi.org/10.1016/0040-6031(76)80009-3	journal	May 1976
[{(C5Me5)Rh(μ-CH2)}2(Me)(η2−CH2CH2)]PF6, a rhodium(IV) ethylene complex Wang, Zhi-Qiang; Turner, Michael L.; Taylor, Brian F. Polyhedron, Vol. 14, Issue 19 https://doi.org/10.1016/0277-5387(95)00277-Y	journal	September 1995
Caesium hexachlororhodate(IV): An authentic compound of rhodium(IV) Ellison, Ian J.; Gillard, R. D. Polyhedron, Vol. 15, Issue 2 https://doi.org/10.1016/0277-5387(95)96713-W	journal	January 1996
Crystal structure and electrochemical behavior of Rh polypyridyl complexes Kim, Mee Y.; Seok, Won K.; Dong, Yongkwan Inorganica Chimica Acta, Vol. 319, Issue 1-2 https://doi.org/10.1016/S0020-1693(01)00433-9	journal	July 2001
The electron spin resonance spectra of the prototype superoxo-dirhodium(III,III) salt Edwards, Nicola S. A.; Ellison, Ian J.; Gillard, R. D. Polyhedron, Vol. 12, Issue 4 https://doi.org/10.1016/S0277-5387(00)81740-4	journal	February 1993
The stability of organometallic ligands in oxidation catalysis Crabtree, Robert H. Journal of Organometallic Chemistry, Vol. 751 https://doi.org/10.1016/j.jorganchem.2013.07.061	journal	February 2014
Synthesis, structure and electrochemical properties of tris-picolinate complexes of rhodium and iridium Basu, Semanti; Peng, Shie-Ming; Lee, Gene-Hsiang Polyhedron, Vol. 24, Issue 1 https://doi.org/10.1016/j.poly.2004.10.015	journal	January 2005
Diminished Electron Transfer Kinetics for [Ru(NH ₃ ) ₆ ] ^3+/2+ , [α-SiW ₁₂ O ₄₀ ] ^4–/5– , and [α-SiW ₁₂ O ₄₀ ] ^5–/6– Processes at Boron-Doped Diamond Electrodes Bano, Kiran; Zhang, Jie; Bond, Alan M. The Journal of Physical Chemistry C, Vol. 119, Issue 22 https://doi.org/10.1021/acs.jpcc.5b02642	journal	May 2015
Electrochemical parametrization of metal complex redox potentials, using the ruthenium(III)/ruthenium(II) couple to generate a ligand electrochemical series Lever, A. B. P. Inorganic Chemistry, Vol. 29, Issue 6, p. 1271-1285 https://doi.org/10.1021/ic00331a030	journal	March 1990
Comparison of the [M(IV)(RR'dtc)3]+M(III)(RR'dtc)3 and [M(IV)(Et2dsc)3]+/M(III)(Et2dsc)3 (M = cobalt, rhodium, iridium; dtc = dithiocarbamate; dsc = diselenocarbamate) redox couples and the reactivity of the oxidation state (IV) complexes in solution and in the gas phase as studied by electrochemical and mass spectrometric techniques Bond, Alan M.; Colton, Ray; Mann, Desma R. Inorganic Chemistry, Vol. 29, Issue 23 https://doi.org/10.1021/ic00348a016	journal	November 1990
Nitrous Acid as a Source of NO and NO ₂ in the Reaction with a Macrocyclic Superoxorhodium(III) Complex Pestovsky, Oleg; Bakac, Andreja Inorganic Chemistry, Vol. 41, Issue 4 https://doi.org/10.1021/ic011018t	journal	February 2002
Generation and Reactivity of Rhodium(IV) Complexes in Aqueous Solutions Pestovsky, Oleg; Bakac, Andreja Inorganic Chemistry, Vol. 41, Issue 15 https://doi.org/10.1021/ic0256415	journal	July 2002
Reaction of Nitrogen Monoxide with a Macrocyclic Superoxorhodium(III) Complex Produces an Observable Nitratorhodium Intermediate Pestovsky, Oleg; Bakac, Andreja Journal of the American Chemical Society, Vol. 124, Issue 8 https://doi.org/10.1021/ja016747m	journal	February 2002
Synthesis and Characterization of Facial and Meridional Tris-cyclometalated Iridium(III) Complexes Tamayo, Arnold B.; Alleyne, Bert D.; Djurovich, Peter I. Journal of the American Chemical Society, Vol. 125, Issue 24 https://doi.org/10.1021/ja034537z	journal	June 2003
A Cationic Rh(III) Complex That Efficiently Catalyzes Hydrogen Isotope Exchange in Hydrosilanes Campos, Jesús; Esqueda, Ana C.; López-Serrano, Joaquín Journal of the American Chemical Society, Vol. 132, Issue 47 https://doi.org/10.1021/ja108521b	journal	December 2010
Distinguishing Homogeneous from Heterogeneous Catalysis in Electrode-Driven Water Oxidation with Molecular Iridium Complexes Schley, Nathan D.; Blakemore, James D.; Subbaiyan, Navaneetha K. Journal of the American Chemical Society, Vol. 133, Issue 27 https://doi.org/10.1021/ja2004522	journal	July 2011
Rapid C–H Bond Activation by a Monocopper(III)–Hydroxide Complex Donoghue, Patrick J.; Tehranchi, Jacqui; Cramer, Christopher J. Journal of the American Chemical Society, Vol. 133, Issue 44 https://doi.org/10.1021/ja207882h	journal	November 2011
Development of a Generic Mechanism for the Dehydrocoupling of Amine-Boranes: A Stoichiometric, Catalytic, and Kinetic Study of H ₃ B·NMe ₂ H Using the [Rh(PCy ₃ ) ₂ ] ⁺ Fragment Sewell, Laura J.; Lloyd-Jones, Guy C.; Weller, Andrew S. Journal of the American Chemical Society, Vol. 134, Issue 7 https://doi.org/10.1021/ja2112965	journal	February 2012
Particle Formation during Oxidation Catalysis with Cp* Iridium Complexes Hintermair, Ulrich; Hashmi, Sara M.; Elimelech, Menachem Journal of the American Chemical Society, Vol. 134, Issue 23 https://doi.org/10.1021/ja3033026	journal	May 2012
Precursor Transformation during Molecular Oxidation Catalysis with Organometallic Iridium Complexes Hintermair, Ulrich; Sheehan, Stafford W.; Parent, Alexander R. Journal of the American Chemical Society, Vol. 135, Issue 29 https://doi.org/10.1021/ja4048762	journal	July 2013
Electrochemical Activation of Cp* Iridium Complexes for Electrode-Driven Water-Oxidation Catalysis Thomsen, Julianne M.; Sheehan, Stafford W.; Hashmi, Sara M. Journal of the American Chemical Society, Vol. 136, Issue 39 https://doi.org/10.1021/ja5068299	journal	September 2014
Stable Iridium(IV) Complexes of an Oxidation-Resistant Pyridine-Alkoxide Ligand: Highly Divergent Redox Properties Depending on the Isomeric Form Adopted Shopov, Dimitar Y.; Rudshteyn, Benjamin; Campos, Jesús Journal of the American Chemical Society, Vol. 137, Issue 22 https://doi.org/10.1021/jacs.5b04185	journal	June 2015
Redox-Noninnocent Behavior of Tris(2-pyridylmethyl)amine Bound to a Lewis Acidic Rh(III) Ion Induced by C–H Deprotonation Kotani, Hiroaki; Sugiyama, Takumi; Ishizuka, Tomoya Journal of the American Chemical Society, Vol. 137, Issue 35 https://doi.org/10.1021/jacs.5b06237	journal	August 2015
Identification of an iridium-containing compound with a formal oxidation state of IX Wang, Guanjun; Zhou, Mingfei; Goettel, James T. Nature, Vol. 514, Issue 7523 https://doi.org/10.1038/nature13795	journal	October 2014
A molecular catalyst for water oxidation that binds to metal oxide surfaces Sheehan, Stafford W.; Thomsen, Julianne M.; Hintermair, Ulrich Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7469	journal	March 2015
Carbon–hydrogen (C–H) bond activation at Pd ^IV : a Frontier in C–H functionalization catalysis Topczewski, Joseph J.; Sanford, Melanie S. Chemical Science, Vol. 6, Issue 1 https://doi.org/10.1039/C4SC02591A	journal	January 2015
Oxidants containing rhodium Ellison, Ian J.; Gillard, R. D. Journal of the Chemical Society, Chemical Communications, Issue 11 https://doi.org/10.1039/c39920000851	journal	January 1992
Synthesis and characterisation of disubstituted di-µ-methylene-bis(η-pentamethylcyclopentadienyl)dirhodium( IV ) complexes; X-ray structure of [{(C ₅ Me ₅ )Rh} ₂ (µ-CH ₂ ) ₂ (CO) ₂ ] ²⁺ Isobe, Kiyoshi; Okeya, Seichi; Meanwell, Neil J. J. Chem. Soc., Dalton Trans., Issue 6 https://doi.org/10.1039/dt9840001215	journal	January 1984
The reactions of di-µ-methylene-bis(pentamethylcyclopentadienyl)-dirhodium( IV ) complexes with benzylmagnesium chloride and with alkynylmagnesium chloride; X-ray structure of [(η ⁵ -C ₅ Me ₅ )Rh(CH ₂ Ph)(µ-CH ₂ ) ₂ Rh(η ⁴ -C ₅ Me ₅ CH ₂ Ph)] Meanwell, Neil J.; Smith, Arnold J.; Maitlis, Peter M. J. Chem. Soc., Dalton Trans., Issue 7 https://doi.org/10.1039/dt9860001419	journal	January 1986
Sr _{4 –x} Ca _x RhO ₆ : a magnetically ordered Rh ^IV compound Vente, Jaap F.; Lear, Janet K.; Battle, Peter D. J. Mater. Chem., Vol. 5, Issue 11 https://doi.org/10.1039/jm9950501785	journal	January 1995
Si–H and Si–C Bond Activation of a Triorganosilane Promoted by [RhCl{P( i -Pr) ₃ } ₂ ]. Synthesis and Structure of a Dinuclear Rh(IV) Complex with μ -Silylene Ligands Osakada, Kohtaro; Koizumi, Take-aki; Yamamoto, Takakazu Bulletin of the Chemical Society of Japan, Vol. 70, Issue 1 https://doi.org/10.1246/bcsj.70.189	journal	January 1997

Cited By (7)

Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O-Donor Organic Ligand Sharninghausen, Liam S.; Sinha, Shashi Bhushan; Shopov, Dimitar Y. Angewandte Chemie, Vol. 129, Issue 42 https://doi.org/10.1002/ange.201707593	journal	September 2017
Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O-Donor Organic Ligand Sharninghausen, Liam S.; Sinha, Shashi Bhushan; Shopov, Dimitar Y. Angewandte Chemie International Edition, Vol. 56, Issue 42 https://doi.org/10.1002/anie.201707593	journal	September 2017
Catalytic Oxygen Evolution from Manganese Complexes with an Oxidation-Resistant N,N,O-Donor Ligand Michaelos, Thoe K.; Lant, Hannah M. C.; Sharninghausen, Liam S. ChemPlusChem, Vol. 81, Issue 10 https://doi.org/10.1002/cplu.201600353	journal	October 2016
N,N,O Pincer Ligand with a Deprotonatable Site That Promotes Redox-Leveling, High Mn Oxidation States, and a Mn ₂ O ₂ Dimer Competent for Catalytic Oxygen Evolution : N,N,O Pincer Ligand with a Deprotonatable Site That Promotes Redox-Leveling, High Mn Oxidation States, and a Mn2O2 Dimer Competent for Catalytic Oxyge Lant, Hannah M. C.; Michaelos, Thoe K.; Sharninghausen, Liam S. European Journal of Inorganic Chemistry, Vol. 2019, Issue 15 https://doi.org/10.1002/ejic.201801343	journal	January 2019
A full set of iridium( iv ) pyridine-alkoxide stereoisomers: highly geometry-dependent redox properties Shopov, Dimitar Y.; Rudshteyn, Benjamin; Campos, Jesús Chemical Science, Vol. 8, Issue 2 https://doi.org/10.1039/c6sc03758e	journal	January 2017
Synthesis of pyridine-alkoxide ligands for formation of polynuclear complexes Shopov, Dimitar Y.; Sharninghausen, Liam S.; Sinha, Shashi Bhushan New Journal of Chemistry, Vol. 41, Issue 14 https://doi.org/10.1039/c7nj01845b	journal	January 2017
Preparation of a rhodium( iii ) cis -diaquacomplex by protic acid induced oxalate-release from mer -[Rh(C ₂ O ₄ )Cl(py) ₃ ] Vasilchenko, Danila; Tkachev, Sergey; Baidina, Iraida New Journal of Chemistry, Vol. 42, Issue 24 https://doi.org/10.1039/c8nj04264k	journal	January 2018

Figures / Tables (7)

Similar Records

Stable Iridium(IV) Complexes of an Oxidation-Resistant Pyridine-Alkoxide Ligand: Highly Divergent Redox Properties Depending on the Isomeric Form Adopted

Journal Article · Tue May 19 00:00:00 EDT 2015 · Journal of the American Chemical Society · OSTI ID:1385948

Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O-Donor Organic Ligand

Journal Article · Wed Aug 16 00:00:00 EDT 2017 · Angewandte Chemie (International Edition) · OSTI ID:1470376

A Pyridine Alkoxide Chelate Ligand That Promotes Both Unusually High Oxidation States and Water-Oxidation Catalysis

Journal Article · Tue Mar 07 23:00:00 EST 2017 · Accounts of Chemical Research · OSTI ID:1345056

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
bio-inspired
catalysis (heterogeneous)
catalysis (homogeneous)
charge transport
coordination compounds
defects
electrodes - solar
electron paramagnetic resonance spectroscopy
hydrogen and fuel cells
ligands
materials and chemistry by design
molecular structure
optics
photosynthesis (natural and artificial)
solar (fuels)
solar (photovoltaic)
spin dynamics
membrane
synthesis (novel materials)
synthesis (self-assembly)
transition metals

CCDC 1437689: Experimental Crystal Structure Determination Sinha, Shashi B.; Shopov, Dimitar Y.; Sharninghausen, Liam S. https://doi.org/10.5517/cc1k812y The current record is supplemented by this dataset	dataset	January 2016
CCDC 1437690: Experimental Crystal Structure Determination Sinha, Shashi B.; Shopov, Dimitar Y.; Sharninghausen, Liam S. https://doi.org/10.5517/cc1k813z The current record is supplemented by this dataset	dataset	January 2016
CCDC 1437691: Experimental Crystal Structure Determination Sinha, Shashi B.; Shopov, Dimitar Y.; Sharninghausen, Liam S. https://doi.org/10.5517/cc1k8140 The current record is supplemented by this dataset	dataset	January 2016

A Stable Coordination Complex of Rh(IV) in an N,O-Donor Environment

Citation Formats

References (36)

Cited By (7)

Linked Research (3)

Figures / Tables (7)

Similar Records

Related Subjects