Synthesis and reactions of heterodinuclear organopalladium–cobalt complexes acting as copolymerization catalyst for aziridine and carbon monoxide

Tanaka, Shin‐ichi; Hoh, Hideko; Akahane, Yoshifumi; Tsutsuminai, Susumu; Komine, Nobuyuki; Hirano, Masafumi; Komiya, Sanshiro

doi:10.1016/j.jorganchem.2006.04.044

Cited by 15 publications

(9 citation statements)

References 30 publications

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“…Ag(I) lowers the relative energies of these TSs through intermetallic cooperativity, which has also been suggested in the case of other heterobimetallic complexes . Analogous to Pd(II)–Ag(I), other d 8 –d 10 interactions between two transition metals have also been observed in both experimental and computational studies . Furthermore, we have identified orbital interaction between palladium- and silver-centered orbitals as well as bond critical point between the metals using Atoms-In-Molecule (AIM) analysis…”

Section: Results and Discussionsupporting

confidence: 59%

Palladium–Silver Cooperativity in an Aryl Amination Reaction through C–H Functionalization

Sunoj

Schaefer

2015

ACS Catal.

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The mechanism of palladium-acetate-catalyzed ortho-amination of N-arylbenzamides by using O-benzoyl hydroxylpiperidine [PhCOON(C5H10)] has been examined by using DFT(M06, B3LYP) computational methods. Particular emphasis is placed on the role of additives such as cesium fluoride and silver acetate. The lowest-energy pathway has been identified by carefully examining 15 or more configurationally different possibilities in each important step of the reaction. The key mechanistic events include (i) the aryl C–H activation of the substrate through a cyclometalation deprotonation; (ii) N–O activation of the reactant PhCOONR2 (where −NR2 = pypiridyl); and (iii) reductive elimination wherein the −N(C5H10) substituent gets transferred to the substrate. A heterobimetallic active species [Pd(μ-OAc)3Ag] is identified as catalytically superior over the conventionally proposed monometallic palladium acetate. A cooperative interaction between Pd(II) and Ag(I) is found to offer additional stabilization to the transition states and intermediates, as compared to those devoid of such an interaction. The second additive, CsF, helps in the deprotonation of the amidic nitrogen as well as offers electrostatic stabilization to intermediates and transition states, thereby influencing the energetics of the reaction. Our findings clearly suggest that refined transition-state models inclusive of additives are highly desirable toward identifying the most preferred mechanistic pathways.

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Section: Results and Discussionsupporting

confidence: 59%

Palladium–Silver Cooperativity in an Aryl Amination Reaction through C–H Functionalization

Sunoj

Schaefer

2015

ACS Catal.

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“…Co/Pd complexes 34a-g (Fig. 8 , Co-Pd distances ≈ 2.6 Å) are the only heterometallic catalysts reported for aziridine/CO ROCOP 109 . 34a exhibited the highest activity for both substituted and non-substituted aziridines, yielding 69% copolymer from 2-methylaziridine in 6 h at 100 °C and 50 bar CO pressure ( Đ = 1.5; 1 mol% catalyst).…”

Section: Ring-opening Polymerisationmentioning

confidence: 98%

“… Proposed heterometallic mechanism for complexes 34a-g along with targeted poly(β-peptide) product and potential side-products from aziridine/CO ROCOP 109 . …”

Section: Ring-opening Polymerisationmentioning

confidence: 99%

Advances in heterometallic ring-opening (co)polymerisation catalysis

2021

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Truly sustainable plastics require renewable feedstocks coupled with efficient production and end-of-life degradation/recycling processes. Some of the most useful degradable materials are aliphatic polyesters, polycarbonates and polyamides, which are often prepared via ring-opening (co)polymerisation (RO(CO)P) using an organometallic catalyst. While there has been extensive research into ligand development, heterometallic cooperativity offers an equally promising yet underexplored strategy to improve catalyst performance, as heterometallic catalysts often exhibit significant activity and selectivity enhancements compared to their homometallic counterparts. This review describes advances in heterometallic RO(CO)P catalyst design, highlighting the overarching structure-activity trends and reactivity patterns to inform future catalyst design.

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“…These reactions are closely related to the reactions of carbonyl metal hydrides and aziridine to give β‐amino‐acyl chelates (Equation (22)) 150–153. Other complexes which catalyze the reactions of aziridines with CO under mild conditions are heterodinuclear palladium‐cobalt compounds ( R )L 2 Pd–Co(CO) 4 ( R = Me, COMe) 154,155. The catalytic activity of there heterodinuclear Pd–Co complexes is higher than that of Jia ’s mononuclear cobalt acyl complexes.…”

Section: Synthesis Of Poly‐β‐peptides and Poly‐β‐peptoids Or Of Pmentioning

confidence: 99%

“…The catalytic activity of there heterodinuclear Pd–Co complexes is higher than that of Jia ’s mononuclear cobalt acyl complexes. Reaction of (dppe)(Me)Pd–Co(CO) 4 with aziridine afforded a cationic aziridine complex with Co(CO) 4 – as anion ( 15 ), which presumably is the starting complex for catalysis 155…”

Section: Synthesis Of Poly‐β‐peptides and Poly‐β‐peptoids Or Of Pmentioning

confidence: 99%

Metal Complexes of Biologically Important Ligands, CLXXVI.[1] Formation of Peptides within the Coordination Sphere of Metal Ions and of Classical and Organometallic Complexes and Some Aspects of Prebiotic Chemistry

Beck

2011

Zeitschrift anorg allge chemie

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Synthesis and reactions of heterodinuclear organopalladium–cobalt complexes acting as copolymerization catalyst for aziridine and carbon monoxide

Cited by 15 publications

References 30 publications

Palladium–Silver Cooperativity in an Aryl Amination Reaction through C–H Functionalization

Palladium–Silver Cooperativity in an Aryl Amination Reaction through C–H Functionalization

Advances in heterometallic ring-opening (co)polymerisation catalysis

Metal Complexes of Biologically Important Ligands, CLXXVI.[1] Formation of Peptides within the Coordination Sphere of Metal Ions and of Classical and Organometallic Complexes and Some Aspects of Prebiotic Chemistry

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