Relative affinities of carbonylbis(triphenylphosphine)rhodium(I) and related cations for anionic ligands in dichloromethane

Araghizadeh, Farshid; Branan, Daniel M.; Hoffman, Neil E.; Jones, J. H.; McElroy, E. Andrew; Miller, Nathan C.; Ramage, David L.; Salazar, Anna Battaglia; Young, Sidney H.

doi:10.1021/ic00294a016

Cited by 32 publications

(24 citation statements)

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“…Indeed, it was recently established that for anhydrous media of low polarity (CH 2 Cl 2 and CHCl 3 ), the affinity of the metal center in [(Ph 3 P) 2 Pd(Ph)(X)] for various halogens, X, decreases in the order F > Cl > Br > I. Similar observations were previously made for a series of Rh(I) complexes …”

Section: Resultssupporting

confidence: 71%

Synthesis and Characterization of Organopalladium Complexes Containing a Fluoro Ligand

1998

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The synthesis of organopalladium complexes containing a fluoro ligand, [(Ph3P)2Pd(F)R], is described. Two general synthetic strategies have been developed: (i) neutralization of hydroxo palladium dimers, [(Ph3P)2Pd2(R)2(μ-OH)2] (R = Me or Ph), with TREAT HF ([(HF)3·NEt3]) in the presence of PPh3 and (ii) the ultrasound-promoted exchange between [(Ph3P)2Pd(I)R] and AgF in benzene. It is essential for the synthesis with TREAT HF that no excess of the HF source is used; otherwise, the corresponding bifluorides, [(Ph3P)2Pd(FHF)R], are formed instead. Conducting the I/F exchange in the presence of 5−10% of the corresponding organic iodide, RI, is beneficial for purity of the desired fluoro complexes. All complexes 1 − 10 have been fully characterized by a variety of methods. The fluoro ligand in [(Ph3P)2Pd(F)R] is inert in anhydrous media of low polarity. However, in the presence of trace amounts of water, F ligand exchange is observed. No irreversible hydrolysis of the Pd−F bond takes place as [(Ph3P)2Pd(F)R] remains the only observable (NMR) species in the system. VT NMR studies of various [(Ph3P)2Pd(F)R] in CH2Cl2 saturated with water have been conducted, revealing a push/pull-type, “ambiphilic” mechanism of the H2O-promoted F ligand-exchange process. The Pd−F bond cleavage likely involves nucleophilic attack of water on the metal center, concomitantly occurring with the formation of a hydrogen bond between the fluoro ligand and H2O.

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Section: Resultssupporting

confidence: 71%

Synthesis and Characterization of Organopalladium Complexes Containing a Fluoro Ligand

1998

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“…ν(C-N) and ν(C-O) for Rh(PMe3)2(CO)NCO were obtained from a spectrum of a 2:1 mixture of N(PPh3)2NCO and Rh(PMe3)2(CO)Cl in CH2Cl2. No difference in frequency or absorbance of the carbonyl stretching band was noted for 1:1 and 2:1 mixtures, a fact indicating that the equilibrium lies essentially completely to the iscyanato side (as in the PPh3-based system of ref 16). d For X ) NCO, ν(C-N), asymmetrically coupled to ν(C-O) and ν (Rh-N), is also intense.…”

Section: Resultsmentioning

confidence: 91%

“…The result is surprising, since the isocyanato complex appears by far the most stable of the Rh-(PPh 3 ) 2 (CO)X series. 16 In all computed complexes, the phosphine ligands are bent toward the uninegative ligand X -(a(X-Rh-P) ) 83-87°) due to electrostatic attraction (hydrogens near X -have Mulliken charges of about 0.2 and 0.04 for the PMe 3 and PH 3 complexes, repectively). The substitution of PMe 3 for PH 3 apparently has little effect on this computed angle in the fluoro (83°) and chloro (85-87°) complexes.…”

Section: Resultsmentioning

confidence: 98%

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Structural Investigations of trans-Rh(PY₃)₂(CO)X (X = F, Cl, NCO; Y = H, Me, Ph) Using Density Functional Theory and X-ray Analysis

et al. 1996

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A study of trans-Rh(PY 3 ) 2 (CO)X (X ) F, Cl; Y ) H, Me) and trans-Rh(PH 3 ) 2 (CO)NCO using density functional theory is presented together with the results of new high-resolution, low-temperature x-ray data analysis of trans-Rh(PPh 3 ) 2 (CO)X (X ) F, NCO). In our calculations, we employed the Becke-exchange functional with the Lee, Yang, and Parr correlation functional (B-LYP) and the double-plus polarization basis set (DZP). Our optimized complexes have a slightly distorted square-planar structure with moderate bending of the phosphine ligands toward the uninegative ligand X -. The predicted structures compare favorably with experimental data for trans-Rh(PPh 3 ) 2 (CO)X (X ) F, Cl, NCO). New X-ray data for trans-Rh(PPh 3 ) 2 -(CO)X (X ) F, NCO) clearly indicate a nonlinear configuration of P-Rh-P atoms, in agreement with our calculations. The apparent linear configuration of P-Rh-P atoms recently reported for the structure of the orthorhombic form of trans-Rh(PPh 3 ) 2 (CO)Cl is most likely an artifact resulting from the disorder and symmetry imposed by the space group of the crystal structure. Computationally predicted vibrational frequencies ν(C-O) and ν(C-N) (for X ) NCO) compare well with solution-phase FTIR data.

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“…Halide contents were measured using halide-selective electrodes and were determined to be <100 ppm. Rh(CO)(PPh 3 ) 2 -NO 3 (1) was synthesized using previously reported procedures [38]. Rh(CO) 2 (acac) and Rh(CO)(PPh 3 ) 2 Cl were acquired from Strem Chemicals.…”

Section: Methodsmentioning

confidence: 99%

Promoting effect of ionic liquids on ligand substitution reactions

Sliger¹,

P’Pool²,

Traylor³

et al. 2005

Journal of Organometallic Chemistry

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Relative affinities of carbonylbis(triphenylphosphine)rhodium(I) and related cations for anionic ligands in dichloromethane

Cited by 32 publications

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Synthesis and Characterization of Organopalladium Complexes Containing a Fluoro Ligand

Synthesis and Characterization of Organopalladium Complexes Containing a Fluoro Ligand

Structural Investigations of trans-Rh(PY₃)₂(CO)X (X = F, Cl, NCO; Y = H, Me, Ph) Using Density Functional Theory and X-ray Analysis

Promoting effect of ionic liquids on ligand substitution reactions

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Relative affinities of carbonylbis(triphenylphosphine)rhodium(I) and related cations for anionic ligands in dichloromethane

Cited by 32 publications

References 0 publications

Synthesis and Characterization of Organopalladium Complexes Containing a Fluoro Ligand

Synthesis and Characterization of Organopalladium Complexes Containing a Fluoro Ligand

Structural Investigations of trans-Rh(PY3)2(CO)X (X = F, Cl, NCO; Y = H, Me, Ph) Using Density Functional Theory and X-ray Analysis

Promoting effect of ionic liquids on ligand substitution reactions

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Structural Investigations of trans-Rh(PY₃)₂(CO)X (X = F, Cl, NCO; Y = H, Me, Ph) Using Density Functional Theory and X-ray Analysis