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Radical (NO) and Nonradical (N2O) Reagents Convert a Ruthenium(IV) Nitride to the Same Nitrosyl Complex

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journal contribution
posted on 17.09.2007, 00:00 by 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.