Osmium nitrogen atom transfer

Table 2 Representative kinetic data for the nitrogen atom transfer reactions by osmium(VI) nitrido...

As already indicated, the chemistry of terminal borylene complexes is as yet almost unexplored. In addition to the photochemically induced borylene transfer, which was already discussed in Chapter 3.2, studies of the reactivity of terminal borylene complexes are restricted to two recent reports by Roper.147,148 The base-stabilized borylene complex [Os (=BNHC9H6N)Cl2(CO)(PPh3)2] (26) undergoes a reaction with ethanol to yield the ethoxy(amino)boryl complex [Os B(OEt)NHCgH6N Cl(CO) (PPh3)2] (35) according to Eq. (13) with a 1,2-shift of the quinoline nitrogen atom from the boron to the osmium center. The alcoholysis of 26 indicates that even the boron atom in base-stabilized borylene complexes displays some electrophilic character—a fact already predicted by a theoretical study.117... 

Reduction by hydride transfer (H" = H + 2e ) occurs when the osmium cluster [Os3( -H)2(CO)io] is reacted with a whole variety of organoazides the hydride anion is transferred to the terminal nitrogen atom N3 and a monoanionic organoazide fragment is... 

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