THE formation of N-C bonds via the intermediacy of ruthenium nitrosyl complexes has been described in two instances : (i) the reaction of [Ru (bipyridyl),(NO) XI,+ (X = C1 or NO,) with 'activated' arylamines,l e.g. PhNMe,, when Ru-co-ordinated p-Me,NC,H,NO is formed, and (ii) the radiolysis of [Ru(NH,),(N0)l3+ in solutions containing. ButOH,, when metal-bound Me,C(CH,NO) (OH) is produced. However, by virtue of the use of charged ruthenium nitrosy1 (Received, 29th October 1976; Corn. 1209.) 7 PhCH,Br was chosen as a model substrate since it can presumably form PhCH,NO which, in turn, may tautomerise to the readily 2 Procedures involved a combination of g.l.c., i.r. and lH n.m.r. spectroscopy, and mass spectrometry.

PhCHO, but in amounts smaller than those obtained under CO. In the absence of a metal, NO gas reacts with benzyl bromide in refluxing toluene to give PhCH,NO, (major product, 45%) and small amounts of PhCN, PhCHO, and PhCH,OH. Reaction of [Ru(NO),(PPh,),] with Ph'CH,CI and other alkyl b r o m i d es, a n d of [ R u ( N 0) , ( P h, P C H , C H , P P h , ) 3 , [ R u ( N 0 ) 1{ P ( 0 P h ) ,},I , [ C o ( N 0) { P ( 0 Et ) ,},I , [Rh(NO) (PPh,),], and [RhCI,(NO)(PPh,),] with PhCH,Br are briefly discussed.

Reaction of the Ru complex (I) with benzyl bromide under CO affords aside the two inorganic complexes (II) and (III) the oxime (IV), cyanide (V), amide (VI), aldehyde (VII), and alcohol (VIII) in amounts depending on reaction temp. and time.

Der Ruthenium‐Komplex (I) und Benzylbromid bilden in heißem Toluol in Gegenwart von Kohlenmonoxid die Komplexe (III) und (IV) sowie die Stickstoff= Verbindungen (V)‐(VII) und geringe Mengen des Aldehydes (VIII) und des Alkoholes (IX).