Rhenium Polyhydride Complexes Containing PhP(CH2CH2CH2PCy2)2(Cyttp):  Protonation, Insertion, and Ligand Substitution Reactions of ReH5(Cyttp) and Structural Characterization of ReH5(Cyttp) and [ReH4(η2-H2)(Cyttp)]SbF6

1996 ◽  
Vol 35 (24) ◽  
pp. 7166-7173 ◽  
Author(s):  
Youhyuk Kim ◽  
Haibin Deng ◽  
Judith C. Gallucci ◽  
Andrew Wojcicki

2019 ◽  
Author(s):  
Pengcheng Wu ◽  
Glenn P. A. Yap ◽  
Klaus Theopold

Chromium(VI) dialkyls are remarkably acidic, yielding a new set of anionic chromium alkylidenes upon deprotonation with KN(TMS)<sub>2</sub>. We describe the characterization of three anionic chromium alkylidenes of the type [(ArN)<sub>2</sub>Cr(=CHR)(CH<sub>2</sub>R]<sup>-</sup> (R = <i><sup>t</sup></i>Bu, SiMe<sub>3</sub>, Ph; Ar = 2,6-diisopropylphenyl). NEt<sub>4</sub>[(ArN)<sub>2</sub>Cr(=CHSiMe<sub>3</sub>)(CH<sub>2</sub>SiMe<sub>3</sub>)] has been structurally characterized by X-ray diffraction. We have also studied the C-H activation of cyclohexane effected by the transient neopentylidene (ArN)<sub>2</sub>Cr(=CHCMe<sub>3</sub>). This reaction generated a tri-nuclear chromium(IV) complex, namely ‘[Cr(NAr)<sub>2</sub>]<sub>3</sub>’, as well as the two organic products cyclohexene and neopentane. A probable intermediate in this reaction could be trapped by PPh<sub>3</sub> to form (ArN)<sub>2</sub>Cr(PPh<sub>3</sub>)<sub>2</sub>. The latter undergoes ligand substitution reactions with ethylene and CO to produce p-acid complexes of tetravalent chromium.



2019 ◽  
Author(s):  
Pengcheng Wu ◽  
Glenn P. A. Yap ◽  
Klaus Theopold

Chromium(VI) dialkyls are remarkably acidic, yielding a new set of anionic chromium alkylidenes upon deprotonation with KN(TMS)<sub>2</sub>. We describe the characterization of three anionic chromium alkylidenes of the type [(ArN)<sub>2</sub>Cr(=CHR)(CH<sub>2</sub>R]<sup>-</sup> (R = <i><sup>t</sup></i>Bu, SiMe<sub>3</sub>, Ph; Ar = 2,6-diisopropylphenyl). NEt<sub>4</sub>[(ArN)<sub>2</sub>Cr(=CHSiMe<sub>3</sub>)(CH<sub>2</sub>SiMe<sub>3</sub>)] has been structurally characterized by X-ray diffraction. We have also studied the C-H activation of cyclohexane effected by the transient neopentylidene (ArN)<sub>2</sub>Cr(=CHCMe<sub>3</sub>). This reaction generated a tri-nuclear chromium(IV) complex, namely ‘[Cr(NAr)<sub>2</sub>]<sub>3</sub>’, as well as the two organic products cyclohexene and neopentane. A probable intermediate in this reaction could be trapped by PPh<sub>3</sub> to form (ArN)<sub>2</sub>Cr(PPh<sub>3</sub>)<sub>2</sub>. The latter undergoes ligand substitution reactions with ethylene and CO to produce p-acid complexes of tetravalent chromium.



2019 ◽  
Vol 48 (18) ◽  
pp. 5987-6002 ◽  
Author(s):  
A. Paden King ◽  
Hendryck A. Gellineau ◽  
Samantha N. MacMillan ◽  
Justin J. Wilson

A subset of fluorinated Co(iii) Schiff base complexes was synthesized, and their structural, ligand exchange, and anticancer properties were investigated.



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