Time-resolved infrared observation of a long-lived transient in the photo-decarbonylation of manganese complex Mn(CO)5C(O)CH3: potential relevance to the CO migratory insertion mechanism

1993 ◽  
Vol 12 (12) ◽  
pp. 4739-4741 ◽  
Author(s):  
William T. Boese ◽  
Brian Lee ◽  
David W. Ryba ◽  
Simon T. Belt ◽  
Peter C. Ford
Keyword(s):  
Manganese Complex ◽  
Time Resolved ◽  
Infrared Observation ◽  
Migratory Insertion ◽  
Insertion Mechanism

scholarly journals First steps towards time-resolved BioXAS at room temperature: state transitions of the manganese complex of oxygenic photosynthesis

2002 ◽  
Vol 9 (5) ◽  
pp. 304-308 ◽  
Author(s):  
Michael Haumann ◽  
Pavel Pospíšil ◽  
Markus Grabolle ◽  
Claudia Müller ◽  
Peter Liebisch ◽  
...  
Keyword(s):  
Room Temperature ◽  
Manganese Complex ◽  
Oxygenic Photosynthesis ◽  
State Transitions ◽  
Time Resolved ◽  
Temperature State

scholarly journals Electrophilic Sulfur Reagent Design Enables Catalytic syn-Carbosulfenylation of Unactivated Alkenes

2021 ◽  
Author(s):  
Zi-Qi Li ◽  
Yilin Cao ◽  
Taeho Kang ◽  
Keary Engle
Keyword(s):  
Reaction Kinetics ◽  
Side Reactions ◽  
Computational Studies ◽  
Transfer Processes ◽  
Leaving Group ◽  
Migratory Insertion ◽  
Component Approach ◽  
Insertion Mechanism ◽  
Weakly Coordinating ◽  
And Control

A multi-component approach to structurally complex organosulfur products is described via the nickel-catalyzed 1,2-carbosulfenylation of unactivated alkenes with organoboron nucleophiles and tailored organosulfur electrophiles. Key to the development of this transformation is the identification of a modular N-alkyl-N-(arylsulfenyl)arenesulfonamide family of sulfur electrophiles. Tuning the electronic and steric properties of the leaving group in these reagents controls pathway selectivity, favoring three-component coupling and suppressing side reactions, as examined via computational studies. The unique syn-stereoselectivity differs from traditional electrophilic sulfenyl transfer processes involving a thiiranium ion intermediate and arises from the directed arylnickel(I) migratory insertion mechanism, as elucidated through reaction kinetics and control experiments. Reactivity and regioselectivity are facilitated by a collection of monodentate, weakly coordinating native directing groups, including sulfonamides, alcohols, amines, amides, and azaheterocycles.

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