Synthesis of chromium(III) bis(benzamidinate) complexes via single electron oxidation

Dykerman, Beth A.; Smith, Joshua J.; McCarvill, Erin M.; Gallant, Amanda J.; Doiron, Natasha D.; Wagner, Brian D.; Jenkins, Hillary A.; Patrick, Brian O.

doi:10.1016/j.jorganchem.2007.01.053

Cited by 7 publications

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“…The formation of bibenzyl suggests that a possible mechanism for the reaction shown in Scheme involves radical species. Many examples of reactions involving the homolytic cleavage of alkyl–halide bonds and atom-transfer processes resulting in the formation of alkyl radicals and metal–halides are described in the literature. − For instance, the anionic pincer complex, [PCP-Pt 0 ] − [PCP = C 6 H 3 (CH 2 P t -Bu 2 ) 2 ], reacts with benzyl chloride in THF and forms PCP-PtCl and bibenzyl . Nevertheless, the detailed mechanism for the conversion shown in Scheme remains to be ascertained.…”

Section: Results and Discussionmentioning

confidence: 99%

Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ²-dmpe)

et al. 2017

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Reaction of Cp*Mo(NO)Cl with 1 equiv of 1,2-bis(dimethylphosphino)ethane (dmpe) in THF at ambient temperature forms [Cp*Mo(NO)(Cl)(κ-dmpe)]Cl (1), which is isolable as an analytically pure yellow powder in 65% yield. Further addition of 2 equiv of CpCo to 1 in CHCl affords dark red Cp*Mo(NO)(κ-dmpe) (2), which was isolated in 36% yield by recrystallization from EtO at -30 °C. Reaction of a benzene solution of 2 with an equimolar amount of elemental sulfur results in the immediate production of dark blue (μ-S)[Cp*Mo(NO)(κ-dmpeS)] (3), which is a rare example of a bimetallic transition-metal complex bridged by only a single sulfur atom and involving Mo═S═Mo bonding. In contrast, reaction of 2 with an excess of sulfur in benzene results in the formation of Cp*Mo(NO)(η-S)(κ-dmpeS) (4). Complex 4 can also be formed by the addition of elemental sulfur to 3, thereby indicating that 3 is a precursor to 4. Cp*Mo(NO)(κ-dmpe) (2) also undergoes interesting transformations when treated with organic bromides. For instance, reaction of 2 with 5 equiv benzyl bromide in THF produces the bimetallic complex (μ-dmpe)[Cp*Mo(NO)Br] (5) and bibenzyl after 4 d at 70 °C probably via radical intermediates. In contrast to its reaction with benzyl bromide, complex 2 forms [Mo(NO)Br(κ-dmpe)] (6), olefin, alkane, and Cp*H when treated with 5 equiv of 1-bromopropane or 1-bromooctane in THF at 70 °C for 72 h. Interestingly, complex 2 does not display any reactivity with bromobenzene or 1-bromoadamantane even after being heated for several days at 70 °C. All new complexes were characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them were established by single-crystal X-ray crystallographic analyses.

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Section: Results and Discussionmentioning

confidence: 99%

Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ²-dmpe)

et al. 2017

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Synthesis and Structure of (TMEDA)Cr(I)2(THF) and [(N,N-DMEDA)2CrI] I

Monillas¹,

Yap²,

Theopold³

2009

J Chem Crystallogr

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Chromium(III) Complexes

Staples

Reinholdt

Mindiola

2021

Comprehensive Coordination Chemistry III

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Synthesis of chromium(III) bis(benzamidinate) complexes via single electron oxidation

Cited by 7 publications

References 78 publications

Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ²-dmpe)

Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ²-dmpe)

Synthesis and Structure of (TMEDA)Cr(I)2(THF) and [(N,N-DMEDA)2CrI] I

Chromium(III) Complexes

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Synthesis of chromium(III) bis(benzamidinate) complexes via single electron oxidation

Cited by 7 publications

References 78 publications

Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ2-dmpe)

Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ2-dmpe)

Synthesis and Structure of (TMEDA)Cr(I)2(THF) and [(N,N-DMEDA)2CrI] I

Chromium(III) Complexes

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Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ²-dmpe)

Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ²-dmpe)