George et ai. / Reactions of Bronioalkanes with Mo(Nr)r(dppe)?Abstract: Bis(dinitrogen)bis[ethylenebis(diphenylphosphine)]molybdenum, Mo(Nz)z(dppe)2 ( l ) , reacts with [ 113Br, nC4H9Br, and (CH3)3CCH2CH2Br, respectively, to form the corresponding 2-alkyldiazenido-A' derivative. MoBr(N2R)-(dppe)l, with loss of 1 equiv of dinitrogen. Reaction of 1 with 6-bromo-1-hexene yields the cyclopentylmethyldiazenido complex, providing support for a radical pathway involving an alkyl radical. Protonation of the alkyldiazenido complexes with aqueous fluoroboric acid produces a 2-alkylhydrazido(2-)-Ar complex [MoBr(NlHR)(dppe)2]BF4 in which the proton is attached to the carbon-bound nitrogen atom. MoBr(NzCdHg)(dppe)2 ( 5 ) forms an adduct with methanol that exhibits physical properties (1R and UV-visible spectra) very similar to those of the corresponding butylhydraido complex suggesting strong hydrogen bonding with methanol. The bromide ion of 5 can be replaced by azide and thiocyanate ion in a metathesis reaction. Reaction of 5 with sodium borohydride or sodium methoxide in benzene-methanol solution at elevated temperature produces almost equal quantities of ammonia and butylamine. Yields approached 60%. Butylmethylamine was also formed in the reactions. Use of ethanol in place of methanol dramatically reduced the yields of ammonia and amine, and MoHl(dppe)z (ca. 24% yield) was identified among the products.

Der Titelkomplex (I) reagiert mit den Alkylbromiden unter Ng‐Eliminierung zu den Bromo‐alkyldiazenido‐Mo‐Komplexen (IIa‐c).