Spin State, Structure, and Reactivity of Terminal Oxo and Dioxygen Complexes of the (PNP)Rh Moiety.

Spin State, Structure, and Reactivity of Terminal Oxo and Dioxygen Complexes of the (PNP)Rh Moiety. Research Abstract Details 

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Spin State, Structure, and Reactivity of Terminal Oxo and Dioxygen Complexes of the (PNP)Rh Moiety. Abstract Text:

[Rh(III)H{(tBu(2)PCH(2)SiMe(2)NSiMe(2)CH(2)PtBu{CMe(2)CH(2)})}], ([RhH(PNP*)]), reacts with O(2) in the time taken to mix the reagents to form a 1:1 eta(2)-O(2) adduct, for which O--O bond length is discussed with reference to the reducing power of [RhH(PNP*)]; DFT calculations faithfully replicate the observed O-O distance, and are used to understand the oxidation state of this coordinated O(2). The reactivity of [Rh(O(2))(PNP)] towards H(2), CO, N(2), and O(2) is tested and compared to the associated DFT reaction energies. Three different reagents effect single oxygen atom transfer to [RhH(PNP*)]. The resulting [RhO(PNP)], characterized at and above -60 degrees C and by DFT calculations, is a ground-state triplet, is nonplanar, and reacts, above about +15 degrees C, with its own tBu C--H bond, to cleanly form a diamagnetic complex, [Rh(OH){N(SiMe(2)CH(2)PtBu(2))(SiMe(2)CH(2)PtBu{CMe(2)CH(2)})}].

Spin State, Structure, and Reactivity of Terminal Oxo and Dioxygen Complexes of the (PNP)Rh Moiety. Publishing Authors By Initials

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Spin State, Structure, and Reactivity of Terminal Oxo and Dioxygen Complexes of the (PNP)Rh Moiety. Journal Published:

PUBLICATION TYPE: Journal Article

Journal: Chemistry (Weinheim an der Bergstrasse, Germany)

VOLUME: 14

Page Numbers: 7680-6

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ISSN: 0947-6539

DAY: 1

MONTH: 09

YEAR: 2008

Spin State, Structure, and Reactivity of Terminal Oxo and Dioxygen Complexes of the (PNP)Rh Moiety. Information

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LANGUAGE: eng

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AFFILIATION: Department of Chemistry, Indiana University, Bloomington, IN and Argonne National Laboratory, Argonne IL (USA), Fax: (+1) 812-855-8300.

Country: Germany

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MEDLINETA: Chemistry

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