Exploring the Reactivity of Four-Coordinate PNPCoX with Access to Three-Coordinate Spin Triplet PNPCo.

Exploring the Reactivity of Four-Coordinate PNPCoX with Access to Three-Coordinate Spin Triplet PNPCo. Research Abstract Details 

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Exploring the Reactivity of Four-Coordinate PNPCoX with Access to Three-Coordinate Spin Triplet PNPCo. Abstract Text:

Michael J Ingleson,Maren Pink,Hongjun Fan,Kenneth G Caulton,Michael J Ingleson,Maren Pink,Hongjun Fan,Kenneth G Caulton,Michael J Ingleson,Maren Pink,Hongjun Fan,Kenneth G Caulton,

The compounds (PNP)CoX, where PNP is (tBu2PCH2SiMe2)2N- and X is Cl, I, N3, OAr, OSO2CF3 and N(H)Ar, are reported. Some of these show magnetic susceptibility, color, and 1H NMR evidence of being in equilibrium between a blue, tetrahedral S = 3/2 state and a red, planar S = 1/2 state; the equilibrium populations are influenced by subtle solvent effects (e.g., benzene and cyclohexane are different), as well as by temperature. Attempted oxidation to Co(III) with O2 occurs instead at phosphorus, giving [P(O)NP(O)]CoX species. The single O-atom transfer reagent PhI=O likewise oxidizes P. Even I2 oxidizes P to give the pendant phosphonium species (tBu2P(I)CH2SiMe2NSiMe2CH2PtBu2)CoI2 with a tetrahedral S = 3/2 cobalt; the solid-state structure shows intermolecular PI...ICo interactions. Attempted alkyl metathesis of PNPCoX inevitably results in reduction, forming PNPCo, which is a spin triplet with planar T-shaped coordination geometry with no agostic interaction. Triplet PNPCo binds N2(weakly) and CO (whose low CO stretching frequency indicates strong PNP --> Co donor power), but not ethene or MeCCMe.

Exploring the Reactivity of Four-Coordinate PNPCoX with Access to Three-Coordinate Spin Triplet PNPCo. Publishing Authors By Initials

MJ Ingleson,M Pink,H Fan,KG Caulton,MJ Ingleson,M Pink,H Fan,KG Caulton,MJ Ingleson,M Pink,H Fan,KG Caulton,

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Exploring the Reactivity of Four-Coordinate PNPCoX with Access to Three-Coordinate Spin Triplet PNPCo. Journal Published:

PUBLICATION TYPE: Journal Article

Journal: Inorganic chemistry

VOLUME: 46

Page Numbers: 10321-34

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ISSN: 0020-1669

DAY: 23

MONTH: 10

YEAR: 2007

Exploring the Reactivity of Four-Coordinate PNPCoX with Access to Three-Coordinate Spin Triplet PNPCo. Information

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LANGUAGE: eng

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Grant and Affiliation Information for Exploring the Reactivity of Four-Coordinate PNPCoX with Access to Three-Coordinate Spin Triplet PNPCo.

AFFILIATION: Department of Chemistry, Indiana University, Bloomington, Indiana 47405.

Country: United States

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MEDLINETA: Inorg Chem

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