In:
Chemistry – A European Journal, Wiley, Vol. 24, No. 57 ( 2018-10-12), p. 15190-15194
Abstract:
The reaction of [V(PS3“)] − ( 1 ) (PS3”=[P(C 6 H 3 ‐3‐Me 3 Si‐2‐S) 3 ] 3− ) with H 2 O led to the formation of [V IV (PS3“)(PS2”S H )] − ( 2 ) (PS2“S H =[P(C 6 H 3 ‐3‐Me 3 Si‐2‐S) 2 (C 6 H 3 ‐3‐Me 3 Si‐2‐SH)] 2− ), indicating a hydrogen atom transfer from H 2 O to a bound thiolate in 1 . Furthermore, the reaction of 1 with CH 3 OH gave the generation of complexes 2 and 3 , [V IV (PS3”)(PS2“S CH3 )] − (PS2”S CH3 =[P(C 6 H 3 ‐3‐Me 3 Si‐2‐S) 2 (C 6 H 3 ‐3‐Me 3 Si‐2‐SCH 3 )] 2− ), implying that C−O and O−H bonds are cleaved by 1 . Quantum mechanical calculations were performed to provide the mechanistic understanding for the reactivity of 1 with water. A key transition state with a lower kinetic barrier is identified. It involves an O−H bond cleavage by a dissociated thiyl radical with an interaction between an OH group and a neighboring bound sulfur donor. To our knowledge, the reactivity of 1 represents a new mode for water activation conducted through cooperation between a metal‐stabilized thiyl radical and a neighboring thiolato donor.
Type of Medium:
Online Resource
ISSN:
0947-6539
,
1521-3765
DOI:
10.1002/chem.201803431
Language:
English
Publisher:
Wiley
Publication Date:
2018
detail.hit.zdb_id:
1478547-X
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