Reversible Activation of Water by an Air‐ and Moisture‐Stable Frustrated Rhodium Nitrogen Lewis Pair

Carmona, María; Ferrer, Joaquina; Rodrı́guez, Ricardo; Passarelli, Vincenzo; Lahoz, Fernando J.; Garcı́a-Orduña, Pilar; Cañadillas‐Delgado, Laura; Carmona, Daniel

doi:10.1002/chem.201902452

Cited by 16 publications

(23 citation statements)

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“…There is no significant chemical difference to be remarked when comparing the structural parameters of the cations of the two complexes. For more detailed data about the molecular structure of the rhodium complex 3 , see ref ( 21 ). Figure 4 shows a view of the two crystallographically independent, but chemically equivalent, cations ( A and B ) found in the asymmetric unit of iridium complex 4 .…”

Section: Resultsmentioning

confidence: 99%

“…The molecular structure of complex 5 corroborates all these features. 21 The compound crystallizes as a racemate in the P2 1 /n space group of the monoclinic system with one solvent molecule in the asymmetric unit ( 5·CD 4 O ). The R Rh enantiomer is depicted in Figure 5 .…”

Section: Resultsmentioning

confidence: 99%

“…Also, deuteration was evidenced by the determination of the crystal structure of 3 - d 15 by low-temperature single crystal neutron-diffraction experiments. 21 During the deuteration process, only isotopologues of compound 3 at different degrees of deuteration are detected by NMR spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

“…Part of this work has been previously communicated. 21 Herein, we extend our study to the iridium homologue complex 4 . Moreover, the reaction of complexes 3 and 4 with alcohols as well as orthometalation reactions, involving new C(sp 3 )–H, O–H and C(sp 2 )–H activations, is also included.…”

Section: Introductionmentioning

confidence: 93%

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Activation of H–H, HO–H, C(sp²)–H, C(sp³)–H, and RO–H Bonds by Transition-Metal Frustrated Lewis Pairs Based on M/N (M = Rh, Ir) Couples

et al. 2022

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Reaction of the dimers [(Cp*MCl) 2 (μ-Cl) 2 ] (Cp* = η 5 -C 5 Me 5 ) with Ph 2 PCH 2 CH 2 NC(NH( p -Tolyl)) 2 ( H 2 L ) in the presence of NaSbF 6 affords the chlorido complexes [Cp*MCl(κ 2 N , P - H 2 L )][SbF 6 ] (M = Rh, 1 ; Ir, 2 ). Upon treatment with aqueous NaOH, solutions of 1 and 2 yield the corresponding complexes [Cp*M(κ 3 N , N′ , P - HL )][SbF 6 ] (M = Rh, 3 ; Ir, 4 ) in which the ligand HL presents a fac κ 3 N , N′ , P coordination mode. Treatment of THF solutions of complexes 3 and 4 with hydrogen gas, at room temperature, results in the formation of the metal hydrido-complexes [Cp*MH(κ 2 N , P - H 2 L )][SbF 6 ] (M = Rh, 5 ; Ir, 6 ) in which the N( p -Tolyl) group has been protonated. Complexes 3 and 4 react with deuterated water in a reversible fashion resulting in the gradual deuteration of the Cp* group. Heating at 383 K THF/H 2 O solutions of the complexes 3 and 4 affords the orthometalated complexes [Cp*M(κ 3 C , N , P - H 2 L -H )][SbF 6 ] [M = Rh, 7 ; Ir, 8 , H 2 L -H = Ph 2 PCH 2 CH 2 NC(NH( p -Tolyl))(NH(4-C 6 H 3 Me))], respectively. At 333 K, complexes 3 and 4 react in THF with methanol, primary alcohols, or 2-propanol giving the metal-hydrido complexes 5 and 6 , respectively. The reaction involves the acceptorless dehydrogenation of the alcohols at a relatively low temperature, without the assistance of an...

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 93%

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Activation of H–H, HO–H, C(sp²)–H, C(sp³)–H, and RO–H Bonds by Transition-Metal Frustrated Lewis Pairs Based on M/N (M = Rh, Ir) Couples

et al. 2022

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“…In this context, we have recently communicated the preparation of the rhodium‐guanidinato complex I ( Scheme 1 ,A ) in which one of the guanidinate nitrogen atoms bears an ethylene‐diphenylphosphane substituent. Complex I behaves as a ‘dormant’ frustrated Lewis pair (FLP) [38–40] able to reversibly activate polar, H−OH, and nonpolar, H−H, bonds showing FLP mechanisms [41] . The FLP behavior of complex I can be anticipated by analyzing its structural features.…”

Section: Introductionmentioning

confidence: 99%

Strained Ruthenium Complexes Bearing Tridentate Guanidine‐Derived Ligands

Wilkinson

Viguri

Rodrı́guez

et al. 2021

Helvetica Chimica Acta

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The dimer [{(η6‐p‐cymene)RuCl}2(μ‐Cl)2] (cymene=MeC6H4iPr) reacts with N,N′‐bis(p‐tolyl)‐N′′‐(2‐pyridinylmethyl)guanidine (H2L1) and N,N′‐bis(p‐tolyl)‐N′′‐(2‐diphenylphosphanoethyl)guanidine (H2L2), in the presence of NaSbF6, giving rise to chlorido compounds of formula [(η6‐p‐cymene)RuCl(H2L)][SbF6] (H2L=H2L1 (1), H2L2 (2)) in which the guanidine ligand adopts a κ2 chelate coordination mode. The related ligand (S)‐N,N′‐bis(p‐tolyl)‐N′′‐(1‐isopropyl, 2‐diphenylphosphano ethyl)guanidine (H2L3) affords mixtures of the corresponding chlorido compound [(η6‐p‐cymene)RuCl(H2L3)][SbF6] (3) together with the complexes [(η6‐p‐cymene)RuCl2(H3L3)][SbF6] (4) and [(η6‐p‐cymene)Ru(κ3N,N′,P‐HL3)][SbF6] (10) which contain phosphano‐guanidinium and phosphano‐guanidinate ions acting as monodentate and tridentate ligand, respectively. Compounds 1, 2 and mixture of 3/4/10 react with AgSbF6 rendering the cationic aqua‐complexes [(η6‐p‐cymene)Ru(H2L)(OH2)][SbF6]2 (H2L=H2L1 (5), H2L2 (6), H2L3 (7)). These aqua‐complexes exhibit a temperature‐dependent fluxional process in solution. Experimental NMR studies and DFT theoretical calculations on complex 6 suggest that the process involves the exchange between two rotamers around one of the C−N guanidine bonds. Treatment of 5–7 with NaHCO3 renders the complexes [(η6‐p‐cymene)Ru(κ3N,N′,N′′‐HL1)][SbF6] (8) and [(η6‐p‐cymene)Ru(κ3N,N′,P‐HL)][SbF6] (HL=HL2 (9), HL3 (10)), respectively, in which the HL ligand adopts a fac κ3 coordination mode. The new complexes have been characterized by analytical and spectroscopic means, including the determination of the crystal structures of the compounds 1, 2, 5, 9 and 10, by X‐ray diffractometric methods.

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Reversible Hydride Migration from C₅Me₅ to Rh^I Revealed by a Cooperative Bimetallic Approach

et al. 2020

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The use of cyclopentadienyl ligands in organometallic chemistry and catalysis is ubiquitous, mostly due to their robust spectator role. Nonetheless, increasing examples of non‐innocent behaviour are being documented. Here, we provide evidence for reversible intramolecular C−H activation at one methyl terminus of C5Me5 in [(η‐C5Me5)Rh(PMe3)2] to form a new Rh−H bond, a process so far restricted to early transition metals. Experimental evidence was acquired from bimetallic rhodium/gold structures in which the gold center binds either to the rhodium atom or to the activated Cp* ring. Reversibility of the C−H activation event regenerates the RhI and AuI monometallic precursors, whose cooperative reactivity towards polar E−H bonds (E=O, N), including the N−H bonds in ammonia, can be understood in terms of bimetallic frustration.

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Reversible Activation of Water by an Air‐ and Moisture‐Stable Frustrated Rhodium Nitrogen Lewis Pair

Cited by 16 publications

References 57 publications

Activation of H–H, HO–H, C(sp²)–H, C(sp³)–H, and RO–H Bonds by Transition-Metal Frustrated Lewis Pairs Based on M/N (M = Rh, Ir) Couples

Activation of H–H, HO–H, C(sp²)–H, C(sp³)–H, and RO–H Bonds by Transition-Metal Frustrated Lewis Pairs Based on M/N (M = Rh, Ir) Couples

Strained Ruthenium Complexes Bearing Tridentate Guanidine‐Derived Ligands

Reversible Hydride Migration from C₅Me₅ to Rh^I Revealed by a Cooperative Bimetallic Approach

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Reversible Activation of Water by an Air‐ and Moisture‐Stable Frustrated Rhodium Nitrogen Lewis Pair

Cited by 16 publications

References 57 publications

Activation of H–H, HO–H, C(sp2)–H, C(sp3)–H, and RO–H Bonds by Transition-Metal Frustrated Lewis Pairs Based on M/N (M = Rh, Ir) Couples

Activation of H–H, HO–H, C(sp2)–H, C(sp3)–H, and RO–H Bonds by Transition-Metal Frustrated Lewis Pairs Based on M/N (M = Rh, Ir) Couples

Strained Ruthenium Complexes Bearing Tridentate Guanidine‐Derived Ligands

Reversible Hydride Migration from C5Me5 to RhI Revealed by a Cooperative Bimetallic Approach

Contact Info

Product

Resources

About

Activation of H–H, HO–H, C(sp²)–H, C(sp³)–H, and RO–H Bonds by Transition-Metal Frustrated Lewis Pairs Based on M/N (M = Rh, Ir) Couples

Activation of H–H, HO–H, C(sp²)–H, C(sp³)–H, and RO–H Bonds by Transition-Metal Frustrated Lewis Pairs Based on M/N (M = Rh, Ir) Couples

Reversible Hydride Migration from C₅Me₅ to Rh^I Revealed by a Cooperative Bimetallic Approach