Reactivity of the Radical NO with a Masked Form of 14 Valence Electron (PNP)Rh: Forming Rh(0, I or II)? | Zendy

Verat Alexander Y. | Zendy; Pink Maren | Zendy; Fan Hongjun | Zendy; Fullmer Benjamin C. | Zendy; Telser Joshua | Zendy; Caulton Kenneth G. | Zendy

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Reactivity of the Radical NO with a Masked Form of 14 Valence Electron (PNP)Rh: Forming Rh(0, I or II)?

Author(s) -

Verat Alexander Y.,

Pink Maren,

Fan Hongjun,

Fullmer Benjamin C.,

Telser Joshua,

Caulton Kenneth G.

Publication year - 2008

Publication title -

european journal of inorganic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 0.667

H-Index - 136

eISSN - 1099-0682

pISSN - 1434-1948

DOI - 10.1002/ejic.200800256

Subject(s) - chemistry , disproportionation , reactivity (psychology) , electron paramagnetic resonance , valence (chemistry) , medicinal chemistry , rhodium , catalysis , lewis acids and bases , stereochemistry , photochemistry , organic chemistry , medicine , physics , alternative medicine , pathology , nuclear magnetic resonance

The reaction of NO with [( t Bu 2 PCH 2 SiMe 2 )NSiMe 2 CH 2 P t Bu(CMe 2 CH 2 )]RhH, a functional equivalent of “(PNP)Rh,” rapidly forms (PNP)Rh(N 2 ) and (PNP)Rh(NO)(NO 2 ). Detected intermediates include (PNP)Rh(NO), characterized by its NMR, EPR and IR spectra as well as by DFT calculation, as having the neutral NO‐centered radical Lewis base donating to Rh I . One other intermediate is detected, using a combination of spectroscopic and DFT methods, as containing a nitrite (O–N=O) ligand that is O ‐bound to Rh, giving an overall C s symmetry. The overall reaction is thus the disproportionation of NO catalyzed by Rh I , and the reaction serves to produce nonradical products from radical NO. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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