Low-valent Iron Complexes Stabilised by a Bulky Guanidinate Ligand: Synthesis and Reactivity Studies

A toluene-capped guanidinato iron(i) complex [(Pipiso)Fe(η6-toluene)] (Pipiso = [(DipN)2C(cis-NC5H8Me2-2,6)]–) was prepared by magnesium metal reduction of {[(Pipiso)FeII(µ-Br)]2} in toluene. The reactivity of the closely related FeI–FeI multiply bonded species, {[Fe(μ-Pipiso)]2} towards a range of unsaturated small molecule substrates was investigated, and found to be broadly similar to that of low-valent β-diketiminato iron complexes. That is, its reaction with CO yielded the iron(i) carbonyl complex [(Pipiso)Fe(CO)3], whereas reaction with CO2 formed the same product via an apparent reductive disproportionation of the substrate. In contrast, reaction between {[Fe(μ-Pipiso)]2} and CS2 led to reductive C=S bond cleavage and the isolation of {[(Pipiso)Fe]2(μ-S)(μ-CS)}. Different reactivity was seen with AdN3 (Ad = 1-adamantyl), which was reductively coupled by the iron(i) dimer to give iron(ii) hexaazenyl complex {[(Pipiso)Fe]2(μ-AdN6Ad)}.

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Room Temperature Alkali Metal Reduction of Carbon Dioxide

10.26434/chemrxiv.12665336 ◽

2020 ◽

Author(s):

Lucas A. Freeman ◽

Akachukwu D. Obi ◽

Haleigh R. Machost ◽

Andrew Molino ◽

Asa W. Nichols ◽

...

Keyword(s):

Alkali Metal ◽

Alkali Metals ◽

Room Temperature ◽

Chemical Reduction ◽

Bond Cleavage ◽

Open Shell ◽

Metal Reduction ◽

One Pot ◽

Earth Abundant ◽

Electron Reduction

The reduction of the relatively inert carbon–oxygen bonds of CO2 to access useful CO2-derived organic products is one of the most important fundamental challenges in synthetic chemistry. Facilitating this bond-cleavage using earth-abundant, non-toxic main group elements (MGEs) is especially arduous because of the difficulty in achieving strong inner-sphere interactions between CO2 and the MGE. Herein we report the first successful chemical reduction of CO2 at room temperature by alkali metals, promoted by a cyclic(alkyl)(amino) carbene (CAAC). One-electron reduction of CAAC-CO2 adduct (1) with lithium, sodium or potassium metal yields stable monoanionic radicals clusters [M(CAAC–CO2)]n(M = Li, Na, K, 2-4) and two-electron alkali metal reduction affords open-shell, dianionic clusters of the general formula [M2(CAAC–CO2)]n (5-8). It is notable that these crystalline clusters of reduced CO2 may also be isolated via the “one-pot” reaction of free CO2 with free CAAC followed by the addition of alkali metals – a reductive process which does not occur in the absence of carbene. Each of the products 2-8 were investigated using a combination of experimental and theoretical methods.

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Main-group metal complexes of α-diimine ligands: structure, bonding and reactivity

Dalton Transactions ◽

10.1039/d1dt02120f ◽

2021 ◽

Author(s):

Rong Zhang ◽

Yanchao Wang ◽

Yanxia Zhao ◽

Carl Redshaw ◽

Igor L. Fedushkin ◽

...

Keyword(s):

Metal Complexes ◽

Small Molecule ◽

Main Group ◽

Group Metal ◽

Diimine Ligands ◽

Main Group Metal ◽

Metal Metal ◽

Low Valent

The use of dad (and bian) ligands in the stabilization of main-group complexes, in particular metal–metal-bonded compounds, as well as the small molecule reactivity of these (low-valent) metal complexes, is summarized.

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