Radical (NO) and nonradical (N(2)O) reagents convert a ruthenium(IV) nitride to the same nitrosyl complex.

Radical (NO) and nonradical (N(2)O) reagents convert a ruthenium(IV) nitride to the same nitrosyl complex. Research Abstract Details 

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Radical (NO) and nonradical (N(2)O) reagents convert a ruthenium(IV) nitride to the same nitrosyl complex. Abstract Text:

Amy Walstrom,Maren Pink,Hongjun Fan,John Tomaszewski,Kenneth G Caulton,

The ruthenium(IV) nitride complex (PNP)RuN (PNP = (tBu2PCH2-SiMe2)2N-) reacts rapidly with 2NO to form (PNP)Ru(NO) and N2O, via no detectable intermediate. The linear nitrosyl complex has a planar structure. In a slower reaction, (PNP)RuN reacts with N2O by O-atom transfer (established by 15N labeling) to give the same nitrosyl complex and N2. Density functional theory (B3LYP) calculations show both reactions to be very thermodynamically favorable. Analysis of possible intermediates in each reaction shows that radical (PNP)RuN(NO) has much spin density on nitride N (hence, N2-), while one 2 + 3 metallacycle, (PNP)RuN3O, has the wrong connectivity to form a product. Instead, an intermediate with a doubly bent N2O (hence, a two-electron reduced N-nitrosoimide form) brings the O atom in proximity to the nitride N on the path to a product.

Radical (NO) and nonradical (N(2)O) reagents convert a ruthenium(IV) nitride to the same nitrosyl complex. Publishing Authors By Initials

A Walstrom,M Pink,H Fan,J Tomaszewski,KG Caulton,

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Radical (NO) and nonradical (N(2)O) reagents convert a ruthenium(IV) nitride to the same nitrosyl complex. Journal Published:

PUBLICATION TYPE: Journal Article

Journal: Inorganic chemistry

VOLUME: 46

Page Numbers: 7704-6

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ISSN: 0020-1669

DAY: 18

MONTH: 08

YEAR: 2007

Radical (NO) and nonradical (N(2)O) reagents convert a ruthenium(IV) nitride to the same nitrosyl complex. Information

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LANGUAGE: eng

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

Country: United States

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MEDLINETA: Inorg Chem

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