Cationic palladium(II) complexes of the sterically hindered bis(4-methylthiazolyl)isoindoline (4-Mebti) with neutral group XVI donor ligands

Bröring, Martin; Scheja, Anne

doi:10.1016/j.ica.2011.02.080

Cited by 4 publications

(1 citation statement)

References 29 publications

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“…The compounds Cy2 PCPNi-OC(O)H , Cy2 PCPPd-OC(O)H (which was crystallized as a mixture containing approximately 12% Cy2 PCPPdCl ), tBu2 PCPPd-OC(O)H , Cy2 PSiPNi-OC(O)H , and Cy2 PSiPPd-OC(O)H were characterized by X-ray crystallography (Figures –). While there are several previous examples of crystallographically characterized monomeric Ni formates, ,,, to the best of our knowledge, the Pd complexes represent only the second, third, and fourth crystallographically characterized Pd formates and are the first to be prepared directly from carbon dioxide. The structures of Cy2 PCPNi-OC(O)H and Cy2 PCPPd-OC(O)H are essentially isostructural, and the metal center is in the distorted-square-planar geometry, typical of many PCP-supported complexes .…”

Section: Resultsmentioning

confidence: 93%

Experimental and Computational Studies of the Reaction of Carbon Dioxide with Pincer-Supported Nickel and Palladium Hydrides

et al. 2012

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A series of Ni(II) and Pd(II) hydrides supported by PNP and PCP ligands, including iPr2 PNP (CH3) PdH ( iPr2 PNP (CH3) = N(2-P i Pr 2 -4-MeC 6 H 3 ) 2 ), iPr2 PNP (CH3) NiH, iPr2 PNP (F) PdH ( iPr2 PNP (F) = N(2-P i Pr 2 -4-C 6 H 3 F) 2 ), CyPh PNPPdH ( CyPh PNP = N(2-P(Cy)(Ph)-4-MeC 6 H 3 ) 2 ), tBu2 PCPPdH ( tBu2 PCP = 2,6-C 6 H 3 (CH 2 P t Bu 2 ) 2 ), tBu2 PCPNiH, Cy2 PCPPdH ( Cy2 PCP = 2,6-C 6 H 3 (CH 2 PCy 2 ) 2 ), and Cy2 PCPNiH, were prepared using literature methods. In addition, the new Ni and Pd hydrides Cy2 PSiPMH (M = Ni, Pd; Cy2 PSiP = Si(Me)(2-PCy 2 -C 6 H 4 ) 2 ) supported by PSiP ligands were synthesized. The analogous metal hydride complexes supported by the Ph2 PSiP ligand ( Ph2 PSiP = Si(Me)(2-PPh 2 -C 6 H 4 ) 2 ) could not be prepared. Instead, the Ni(0) and Pd(0)which have been proposed to be in equilibrium with Ph2 PSiPMH (M = Ni, Pd) and PPh 3 , were prepared. Facile carbon dioxide insertion into the metal−hydride bond to form the metal formate complexes tBu2 PCPM-OC(O)H (M = Ni, Pd) or Cy2 PCPM-OC(O)H (M = Ni, Pd) was observed for PCP-supported species, and a similar reaction was observed for Cy2 PSiP-supported hydrides to form Cy2 PSiPM-OC(O)H (M = Ni, Pd).No reaction with carbon dioxide was observed for any complexes supported by PNP ligands. The η 2 -silane complex Ph2 PSi H PPd(PPh 3 ) reacted rapidly with carbon dioxide to give Ph2 PSiPPd-OC(O)H and PPh 3 , while the corresponding Ni complex Ph2 PSi H PNi(PPh 3 ) did not react with carbon dioxide. DFT calculations indicate that carbon dioxide insertion is thermodynamically favorable for PSiP-and PCP-supported hydrides because the strong trans influence of the anionic carbon donor destabilizes the metal−hydride bond. In contrast, carbon dioxide insertion is thermodynamically unfavorable for the PNP-supported species. In the case of the η 2 -silane complexes, carbon dioxide insertion is thermodynamically favorable for Pd and unfavorable for Ni. This is because the equilibrium between the metal hydride and PPh 3 and the η 2 -silane complex more strongly favors the metal hydride for Pd than for Ni. In the cases of metal hydrides, the thermodynamic favorability of carbon dioxide insertion can be predicted from the natural bond orbital charge on the hydride. The pathway for carbon dioxide insertion into the metal hydride is concerted and features a four-centered transition state. The energy of the transition state for carbon dioxide insertion decreases as the trans influence of the anionic donor of the pincer ligand increases.

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Section: Resultsmentioning

confidence: 93%

Experimental and Computational Studies of the Reaction of Carbon Dioxide with Pincer-Supported Nickel and Palladium Hydrides

et al. 2012

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Bis(4‐methylthiazolyl)isoindoline (4‐Mebti) Complexes of Palladium: Cationic [Pd^II(4‐Mebti)L]⁺Species with a L = Neutral Group XIV or Group XV Donor Ligand

Bröring

2011

Zeitschrift anorg allge chemie

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Ligand exchange has been studied on the chlorido palladium(II) complex of the bis(4-methylthiazolylimino)isoindoline ligand, [Pd(4-Mebti)Cl], with a number of neutral group XIV and group XV donor ligands in the presence of the sodium salt of tetrakis[3,5bis(trifluoromethyl)phenyl]borate NaB(Ar F ) 4 . Seven new cationic compounds with L = PMe 3 , tBuNH 2 , PhNH 2 , py, 2,6-Me 2 py, MeCN and MeNC were obtained as B(Ar F ) 4 salts, and were characterized by analytic, spectroscopic and crystallographic means. Further attempts to observe ligand exchange reactions with either the softer AsMe 3 or SbMe 3 donor ligands or with different carbenes were unsuccessful and * Prof. Dr. M. Bröring

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Interactions of acetamide and acrylamide with heme models: Synthesis, infrared spectra, and solid state molecular structures of five- and six-coordinate ferric porphyrin derivatives

Guan

Nguyen

et al. 2019

Journal of Inorganic Biochemistry

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Cationic palladium(II) complexes of the sterically hindered bis(4-methylthiazolyl)isoindoline (4-Mebti) with neutral group XVI donor ligands

Cited by 4 publications

References 29 publications

Experimental and Computational Studies of the Reaction of Carbon Dioxide with Pincer-Supported Nickel and Palladium Hydrides

Experimental and Computational Studies of the Reaction of Carbon Dioxide with Pincer-Supported Nickel and Palladium Hydrides

Bis(4‐methylthiazolyl)isoindoline (4‐Mebti) Complexes of Palladium: Cationic [Pd^II(4‐Mebti)L]⁺Species with a L = Neutral Group XIV or Group XV Donor Ligand

Interactions of acetamide and acrylamide with heme models: Synthesis, infrared spectra, and solid state molecular structures of five- and six-coordinate ferric porphyrin derivatives

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Cationic palladium(II) complexes of the sterically hindered bis(4-methylthiazolyl)isoindoline (4-Mebti) with neutral group XVI donor ligands

Cited by 4 publications

References 29 publications

Experimental and Computational Studies of the Reaction of Carbon Dioxide with Pincer-Supported Nickel and Palladium Hydrides

Experimental and Computational Studies of the Reaction of Carbon Dioxide with Pincer-Supported Nickel and Palladium Hydrides

Bis(4‐methylthiazolyl)isoindoline (4‐Mebti) Complexes of Palladium: Cationic [PdII(4‐Mebti)L]+Species with a L = Neutral Group XIV or Group XV Donor Ligand

Interactions of acetamide and acrylamide with heme models: Synthesis, infrared spectra, and solid state molecular structures of five- and six-coordinate ferric porphyrin derivatives

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Bis(4‐methylthiazolyl)isoindoline (4‐Mebti) Complexes of Palladium: Cationic [Pd^II(4‐Mebti)L]⁺Species with a L = Neutral Group XIV or Group XV Donor Ligand