Strongly Nucleophilic Rh<sup>I</sup> Centre in Square‐Planar Complexes with Terdentate (κ<sup>3</sup>) 2,2′:6′,2′′‐Terpyridine Ligands: Crystallographic, Electrochemical and Density Functional Theoretical Studies

Pater, Boke C. de; Frühauf, Hans‐Werner; Vrieze, K.; Gelder, René de; Baerends, Evert Jan; McCormack, Drew A.; Lutz, Martin; Spek, Anthony L.; Hartl, František

doi:10.1002/ejic.200300699

Cited by 20 publications

(22 citation statements)

References 39 publications

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“…The Rh–C NHC bonds [1.957(6) Å] are slightly shorter than those reported for 2 . In comparison to the recently reported blue Rh(terpy)Cl,15 the corresponding Rh–N pyridine bonds in 9a are longer.…”

Section: Resultscontrasting

confidence: 72%

“…The HOMO–LUMO gap for 2‐dft of 2.92 eV is marginally larger than the gap for 9b‐dft (2.49 eV). For comparison, these values are much larger than the values reported for Rh(terpy)Cl (1.04 eV) 15. It is therefore plausible that this difference may lead to different reactivity of 2 and 9b compared with Rh(terpy)Cl.…”

Section: Resultsmentioning

confidence: 63%

“…The replacement in complex 2 of one NHC by the poorer σ‐donating pyridine group to give 9 is expected to reduce the electron density on the metal atom. However, it should be more electron‐rich than the metal atom in Rh(terpy)Cl 15. In the latter, Rh I has been classified as electron‐rich on the basis of the oxidation potential of the complex, as measured by CV and DFT calculations.…”

Section: Resultsmentioning

confidence: 99%

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“Pincer” N‐Heterocyclic Carbene Complexes of Rhodium Functionalised with Pyridyl and Bipyridyl Donors

et al. 2006

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The “pincer”‐type carbene complexes Rh(C–N–C)Cl and Rh(C–N–N)Cl [C–N–C = 3,3′‐diaryl‐1,1′‐pyridine‐2,6‐diylbis(imidazol‐2‐ylidene), C–N–N = 1‐aryl‐3‐(2,2′‐bipyridin‐6‐yl)imidazol‐2‐ylidene] have been prepared and characterised by spectroscopic and diffraction methods. They bind CO to give cationic complexes but are inert to H2. Both oxidatively add CH2Cl2 to give octahedral RhIII complexes. Theoretical calculations provide insight into the bonding of the Rh(C–N–C)Cl and Rh(C–N–N)Cl complexes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Section: Resultscontrasting

confidence: 72%

Section: Resultsmentioning

confidence: 63%

Section: Resultsmentioning

confidence: 99%

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“Pincer” N‐Heterocyclic Carbene Complexes of Rhodium Functionalised with Pyridyl and Bipyridyl Donors

et al. 2006

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“…The broad visible bands are similar to the metal-to-ligand charge-transfer (MLCT) transitions observed in rhodium complexes containing π-acceptor ligands [45,46] which the charge transfer character stems from interactions between filled metal d orbitals and antibonding ligand π* orbitals. The MLCT transition is observed to be less favoured for the tetrametallic derivatives being only clearly defined for the dppbz derivative, 5b, probably due to the higher aromaticity and electron deficiency of the system due to the presence of the benzene unit.…”

Section: Photophysical Characterizationmentioning

confidence: 52%

“…The corresponding reaction with dppb gave rise to the formation of different species in equilibrium whose P-NMR signals showed similar chemical shifts, preventing the isolation of pure 3c. Moreover, the rigidity of the alkynyl group of the diphosphine dppa blocks that the diphosphine could act as a chelating ligand and consequently precludes the formation of the mononuclear complex 4c [45,49].…”

Section: Photophysical Characterizationmentioning

confidence: 99%

Rhodium(I) macrocyclic and cage-like structures containing diphosphine bridging ligands

et al. 2016

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Three series of rhodium organometallic complexes, mono-(1c, 2c, 5c, 6c), di-(1a-6a) and tetranuclear (1b, 5b, 6b), containing six different diphosphines (1,1'bis(diphenylphosphino)methane or dppm (1), 1,2-bis(diphenylphosphino)ethane or dppe (2), 1,4-bis(diphenylphosphino)butane or dppb (3), bis(diphenylphosphino)acetylene or dppa (4), 1,2-bis(diphenylphosphino)benzene or dppbz (5) and 4,5-bis(diphenylphosphino)-9,9'-dimethylxanthene or xantphos (6) were successfully synthesised. These Rh(I) complexes were characterised by conventional techniques. The influence of the flexibility/rigidity of these P-donor ligands was carefully analysed, including their effect on both synthesis and catalysis. The luminescent properties of the dinuclear and tetranuclear complexes were investigated and only those containing dppa, dppbz and xantphos displayed luminescence. Structures of dinuclear complexes were modelled by using DFT methods in order to elucidate the most possible conformation. The different types of complexes were applied in the catalytic hydrogenation of (E)-4phenylbut-3-en-2-one, showing high activity and similar catalytic behaviour. No cooperative effect could be inferred.

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Molecular Structures, Reactivity, and NMR Spectroscopic Studies of Cyclic and Non‐cyclic Silyl‐substituted 1, 2‐Dicarba‐closo‐dodecaborane(12) Derivatives

Wrackmeyer

Klimkina

Milius

2012

Zeitschrift anorg allge chemie

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Non-cyclic and cyclic silyl-substituted 1,2-dicarba-closo-dodecaborane(12) derivatives were prepared mainly by salt elimination methods. Several known and new compounds were structurally characterized by X-ray analysis in the solid state and by mulinuclear magnetic resonance ( 1 H, 11 B, 13 C, 29 Si, 77 Se, and 125 Te NMR) in solution. This includes the 1,2-bis(trimethylsilyl) and 1,2-bis(chlorodimethylsilyl) derivatives as examples for non-cyclic compounds and a series of 1,1,3,3-tetramethyl-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3-1080 disila-2-element-cyclopentanes (element = S, Se, Te). Numerous spinspin coupling constants were determined together with their signs. Molecular gas phase geometries for most compounds studied were optimized by calculations [B3Lyp/6-311+G(d,p)], and NMR parameters were calculated at the same level of theory. The conversion of silylsubstituted ortho-carboranes into their respective 7,8-dicarba-nido-undecaborate(1-) derivatives was explored successfully for several examples.In the presented work, we have set out to prepare the missing heavy homologues of 6a with sulfur (6b), selenium (6c) and tellurium (6d), starting from 4 or 5. Some aspects of the reactivity of 5 was addressed, and first attempts were made to convert some of the silyl-substituted carboranes into the respective 7,8-dicarba-nido-undecaborates(1-). The NMR spectra of 3-6 were measured ( 1 H, 11 B, 13 C, 29 Si, 77 Se, and 125 Te NMR), including the determination of absolute signs of spinspin coupling constants, if possible. The molecular structures of 3, 4, 6c, and 6d were determined by X-ray structural analysis, and the gas phase geometries of 3-6 were optimized [B3LYP/6-311+G(d,p)] followed by calculation of NMR parameters at the same level of theory (except of 6d). Results and Discussion Syntheses and NMR SpectroscopyThe synthetic routes are summarized in Scheme 2. Clearly, the dichloride 4 [11] offers great synthetic potential for further transformations. It proved necessary to use the salt elimination reaction of 4 with dilthium selenide [12] or -telluride [12] to obtain pure samples of 6c and in particular of 6d. In principle, the strained four-membered cycle in 5 [8] appears to be attractive for insertion reactions. [7b] However, it does not react with tellurium, it reacts sluggishly with selenium, and somewhat more readily with sulfur. Surprisingly, 5 does not react with bis(trimethylsilyl)peroxide at room temp., whereas its reaction with trimethylamine N-oxide [13] affords the known disiloxane 6a [9,11,14] quantitatively under mild conditions. Silyl-substituted 1,2-Dicarba-closo-dodecaborane(12) Derivatives Scheme 1. Some known 1,2-silyl-substituted ortho-carborane derivatives, obtained from the reactions of 1,2-dilithio-1,2-dicarba-closo-dodecaborane(12) with various chlorosilanes. Scheme 2. Routes to 1,1,3,3-tetramethyl-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3-disila-2-chalkogena-cyclopentanes 6a-6d.The compounds 6b,c,d are crystalline yellowish (6b, 6c) or yellow (6d) solids sensitive to moisture...

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Strongly Nucleophilic Rh^I Centre in Square‐Planar Complexes with Terdentate (κ³) 2,2′:6′,2′′‐Terpyridine Ligands: Crystallographic, Electrochemical and Density Functional Theoretical Studies

Cited by 20 publications

References 39 publications

“Pincer” N‐Heterocyclic Carbene Complexes of Rhodium Functionalised with Pyridyl and Bipyridyl Donors

“Pincer” N‐Heterocyclic Carbene Complexes of Rhodium Functionalised with Pyridyl and Bipyridyl Donors

Rhodium(I) macrocyclic and cage-like structures containing diphosphine bridging ligands

Molecular Structures, Reactivity, and NMR Spectroscopic Studies of Cyclic and Non‐cyclic Silyl‐substituted 1, 2‐Dicarba‐closo‐dodecaborane(12) Derivatives

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Strongly Nucleophilic RhI Centre in Square‐Planar Complexes with Terdentate (κ3) 2,2′:6′,2′′‐Terpyridine Ligands: Crystallographic, Electrochemical and Density Functional Theoretical Studies

Cited by 20 publications

References 39 publications

“Pincer” N‐Heterocyclic Carbene Complexes of Rhodium Functionalised with Pyridyl and Bipyridyl Donors

“Pincer” N‐Heterocyclic Carbene Complexes of Rhodium Functionalised with Pyridyl and Bipyridyl Donors

Rhodium(I) macrocyclic and cage-like structures containing diphosphine bridging ligands

Molecular Structures, Reactivity, and NMR Spectroscopic Studies of Cyclic and Non‐cyclic Silyl‐substituted 1, 2‐Dicarba‐closo‐dodecaborane(12) Derivatives

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Strongly Nucleophilic Rh^I Centre in Square‐Planar Complexes with Terdentate (κ³) 2,2′:6′,2′′‐Terpyridine Ligands: Crystallographic, Electrochemical and Density Functional Theoretical Studies