Platinum(ii) alkyl complexes of chelating dibridgehead diphosphines P((CH2)n)3P (n = 14, 18, 22); facile cis/trans isomerizations interconverting gyroscope and parachute like adducts

Yun Zhu; Andreas Ehnbom; Tobias Fiedler; Yi Shu; Nattamai Bhuvanesh; Michael B. Hall; John A. Gladysz

doi:10.1039/d1dt02321g

Platinum(ii) alkyl complexes of chelating dibridgehead diphosphines P((CH2)n)3P (n = 14, 18, 22); facile cis/trans isomerizations interconverting gyroscope and parachute like adducts

Dalton Transactions ◽

10.1039/d1dt02321g ◽

2021 ◽

Vol 50 (36) ◽

pp. 12457-12477

Author(s):

Yun Zhu ◽

Andreas Ehnbom ◽

Tobias Fiedler ◽

Yi Shu ◽

Nattamai Bhuvanesh ◽

...

Keyword(s):

Alkyl Complexes ◽

Chelate Ligands

The dibridgehead diphosphines P((CH2)n)3P can serve either as cis or trans spanning chelate ligands. Reactions of trans PtCl2 adducts and RLi (2 equiv.) give only cis PtR2 adducts, which upon reaction with HCl (1 equiv.) revert to trans PtRCl adducts.

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Reactivity of TpMe2-Supported Yttrium Alkyl Complexes toward Aromatic N-Heterocycles: Ring-Opening or CC Bond Formation Directed by CH Activation

Chemistry - A European Journal ◽

10.1002/chem.201303608 ◽

2013 ◽

Vol 20 (3) ◽

pp. 867-876 ◽

Cited By ~ 13

Author(s):

Weiyin Yi ◽

Jie Zhang ◽

Shujian Huang ◽

Linhong Weng ◽

Xigeng Zhou

Keyword(s):

Ring Opening ◽

Bond Formation ◽

Alkyl Complexes

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Origins of Enantioselectivity with Nitrogen−Sulfur Chelate Ligands in Palladium-Catalyzed Allylic Substitution

The Journal of Organic Chemistry ◽

10.1021/jo9910177 ◽

1999 ◽

Vol 64 (22) ◽

pp. 8256-8262 ◽

Cited By ~ 44

Author(s):

Harry Adams ◽

James C. Anderson ◽

Rachel Cubbon ◽

Daniel S. James ◽

John P. Mathias

Keyword(s):

Allylic Substitution ◽

Chelate Ligands ◽

Palladium Catalyzed

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Iminoacyl Alkyl Complexes of Zirconium Supported by a Ferrocene-Linked Diphosphinoamide Ligand Scaffold

Australian Journal of Chemistry ◽

10.1071/ch15763 ◽

2016 ◽

Vol 69 (5) ◽

pp. 555 ◽

Cited By ~ 4

Author(s):

Nathan R. Halcovitch ◽

Michael D. Fryzuk

Keyword(s):

General Formula ◽

Mechanistic Studies ◽

Hydrogen Shift ◽

Alkyl Complexes ◽

Rate Determining Step ◽

Zirconium Complexes ◽

Alkyl Derivatives ◽

Benzyl Substituent

Zirconium dialkyl complexes of the general formula fc(NPiPr2)2ZrR2 (where fc = 1,1′-ferrocenyl, R = CH3, CH2Ph, CH2tBu, tBu) have been synthesized and characterized via the addition of alkyl lithium or potassium benzyl derivatives to the dichloride complex fc(NPiPr2)2ZrCl2(THF). Addition of 2,6-dimethylphenylisocyanide to these alkyl derivatives generates the corresponding mono iminoacyl alkyl zirconium complexes. On thermolysis, the iminoacyl moiety containing a benzyl substituent undergoes rearrangement to yield a new complex that contains an alkene-amido fragment. Mechanistic studies point to a 1,2 hydrogen shift as the rate-determining step.

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