DFT calculations of NMR JC–H coupling constants: An additional tool to characterize the α-agostic interaction in high oxidation state M-alkylidene complexes (M=Re, Mo and Ta)

Polyhedron ◽  
2006 ◽  
Vol 25 (2) ◽  
pp. 339-348 ◽  
Author(s):  
Xavier Solans-Monfort ◽  
Odile Eisenstein
Keyword(s):  
Dft Calculations ◽  
Oxidation State ◽  
Coupling Constants ◽  
High Oxidation State ◽  
Additional Tool ◽  
Agostic Interaction ◽  
High Oxidation ◽  
Alkylidene Complexes

scholarly journals High Oxidation State Molybdenum Imido Heteroatom-Substituted Alkylidene Complexes

2013 ◽  
Vol 32 (16) ◽  
pp. 4612-4617 ◽  
Author(s):  
Erik M. Townsend ◽  
Stefan M. Kilyanek ◽  
Richard R. Schrock ◽  
Peter Müller ◽  
Stacey J. Smith ◽  
...  
Keyword(s):  
Oxidation State ◽  
High Oxidation State ◽  
High Oxidation ◽  
Alkylidene Complexes

scholarly journals Bimetallic Cooperativity with a 2-Phosphinoimidazole-Derived Pd(II) Dimer Enables Naphthalene Synthesis via dimeric Pd(III) Catalysis

2020 ◽  
Author(s):  
Chloe C. Ence ◽  
S. Hadi Nazari ◽  
Mariur Rodriguez Moreno ◽  
Manase F. Matu ◽  
Samantha G. Kulka ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Dft Calculations ◽  
Oxidation State ◽  
Methyl Ketone ◽  
Methyl Ketones ◽  
Mechanistic Studies ◽  
High Oxidation State ◽  
Pd Catalysts ◽  
Silver Triflate ◽  
High Oxidation

We report the synthesis of bimetallic Pd(I) and Pd(II) complexes scaffolded on bidentate 2-phosphinoimidazole ligands. These complexes display unique catalytic activity and enable the expeditious formation of 1,3-disubstituted naphthalenes via an unprecedented coupling of aryl iodides and methyl ketones in the presence of silver triflate. Excellent substrate scope for naphthalene formation is also demonstrated. Mechanistic studies suggest that the transformation proceeds via Pd-catalyzed arylation of a methyl ketone, followed by cyclization with a second equivalent of ketone. Importantly, this ketone arylation processes occurs under oxidizing conditions, suggesting involvement of higher oxidation state dimeric Pd catalysts. Based on experiments and DFT calculations, we propose a mechanism involving high oxidation state Pd(III) bimetallic catalysis. These new bimetallic complexes possess reactivity that is not seen with monometallic Pd catalysts and we confirm the importance of the palladium catalyst for both arylation and cyclization for naphthalene formation.

Synthesis of High Oxidation State Bimetallic Alkylidene Complexes for Controlled ROMP Synthesis of Triblock Copolymers

2005 ◽  
Vol 24 (21) ◽  
pp. 5058-5066 ◽  
Author(s):  
Richard R. Schrock ◽  
Andrea J. Gabert ◽  
Rojendra Singh ◽  
Adam S. Hock
Keyword(s):  
Oxidation State ◽  
Triblock Copolymers ◽  
High Oxidation State ◽  
High Oxidation ◽  
Alkylidene Complexes

scholarly journals Bimetallic Cooperativity with a 2-Phosphinoimidazole-Derived Pd(II) Dimer Enables Naphthalene Synthesis via dimeric Pd(III) Catalysis

2020 ◽  
Author(s):  
Chloe C. Ence ◽  
S. Hadi Nazari ◽  
Mariur Rodriguez Moreno ◽  
Manase F. Matu ◽  
Samantha G. Kulka ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Dft Calculations ◽  
Oxidation State ◽  
Methyl Ketone ◽  
Methyl Ketones ◽  
Mechanistic Studies ◽  
High Oxidation State ◽  
Pd Catalysts ◽  
Silver Triflate ◽  
High Oxidation

We report the synthesis of bimetallic Pd(I) and Pd(II) complexes scaffolded on bidentate 2-phosphinoimidazole ligands. These complexes display unique catalytic activity and enable the expeditious formation of 1,3-disubstituted naphthalenes via an unprecedented coupling of aryl iodides and methyl ketones in the presence of silver triflate. Excellent substrate scope for naphthalene formation is also demonstrated. Mechanistic studies suggest that the transformation proceeds via Pd-catalyzed arylation of a methyl ketone, followed by cyclization with a second equivalent of ketone. Importantly, this ketone arylation processes occurs under oxidizing conditions, suggesting involvement of higher oxidation state dimeric Pd catalysts. Based on experiments and DFT calculations, we propose a mechanism involving high oxidation state Pd(III) bimetallic catalysis. These new bimetallic complexes possess reactivity that is not seen with monometallic Pd catalysts and we confirm the importance of the palladium catalyst for both arylation and cyclization for naphthalene formation.

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