Activation of O−H and C−O Bonds in Water and Methanol by a Vanadium‐Bound Thiyl Radical

Abstract

The reaction of [V(PS3")] (1) (PS3"=[P(C H -3-Me Si-2-S) ] ) with H O led to the formation of [V (PS3")(PS2"S )] (2) (PS2"S =[P(C H -3-Me Si-2-S) (C H -3-Me Si-2-SH)] ), indicating a hydrogen atom transfer from H O to a bound thiolate in 1. Furthermore, the reaction of 1 with CH OH gave the generation of complexes 2 and 3, [V (PS3")(PS2"S )] (PS2"S =[P(C H -3-Me Si-2-S) (C H -3-Me Si-2-SCH )] ), 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.

Reversible Activation of Water by an Air‐ and Moisture‐Stable Frustrated Rhodium Nitrogen Lewis Pair

“…Activation of the O−H bond of water constitutes an important step in addressing the challenge of the catalytic functionalization of water and the generation of renewable energy . Activation of water includes strategies, such as oxidative addition to transition‐metal complexes or to main‐group species, metal–ligand cooperative chemistry, O−H bond weakening either via water coordination to a metal center or through the second coordination sphere interaction and σ‐bond metathesis…”

“…porting Information) [17] reveals that the ligand L presents a fack 3 N,N',P coordinationm ode that probably forces the central N(1) atom to adopt ap yramidal geometry (S8N(1) = 327.4(2)8). Accordingly,t he smallN (1)-Rh-N(2) and N(1)-C(25)-N(2) angles, 62.78 (6) and 110.60 (15)8,r espectively,f ar from the ideal hybridization values, reflect the strain of the four-membered metalacycle Rh-N(1)-C(25)-N(2).…”

“…Activation of the OÀHb ond of water constitutes an important step in addressing the challenge of the catalytic functionalization of water and the generation of renewable energy. [1] Activation of water includes strategies, such as oxidative addition to transition-metal complexes [2] or to main-groups pecies, [3] metal-ligand cooperative chemistry, [4] OÀHb ond weakening either via water coordination to am etal center [5] or through the second coordination sphere interaction [6] and s-bond metathesis. [7] On the other hand, the last decade has witnessed the development of an ew class of intra-or intermoleculars ystems in which aL ewis acid and aL ewis base do not yield the classical Lewis acid/base adduct because of steric and/ore lectronic factors.…”

Reversible Conversion of Disulfide/Dithiolate Occurring at a Vanadium(IV) Center: A Biomimetic System for Redox Exchange in Vanabin

“…Complex 3 reported previously has an eight-coordinate vanadium center with a formal charge of +5. In fact, spectroscopic investigation and density function theory calculations provide a more accurate charge distribution, consisting of V V -thiolate and V IV -thiyl radical. , Thus, the first electron reduction of 1 involves a disulfide cleavage to dithiolate with thiyl radical character, concurrently, giving rise to partial oxidation of V IV to V V . The redox couple at −1.29 V is related to one-electron reduction of 3 to [V IV (PS3″) 2 ] 2– ( 4 ), an eight-coordinate V IV complex that is confirmed by chemical reduction and spectroscopic observation (vide infra).…”

Ligand-Based Reactivity of Oxygenation and Alkylation in Cobalt Complexes Binding with (Thiolato)phosphine Derivatives

“…(Thiolato)­phosphine ligand derivatives have shown a noninnocent nature in several well-defined metal complexes. ,, From this perspective, the reactivity of cobalt complexes with several (thiolato)­phosphine derivatives were explored (Chart ). In this particular study, a four-coordinate square-planar Co II complex, Co­(PS1″) 2 ( 1 ) ([PS1″] − = [P­(Ph) 2 (C 6 H 3 -3-SiMe 3 -2-S)] − ), and an octahedral Co III thiolate complex, [NEt 4 ]­[Co­(PS2*) 2 ] ( 3 ) ([PS2*] 2– = [P­(Ph)­(C 6 H 3 -3-Ph-2-S) 2 ] 2– ), were isolated and characterized.…”