Reactivity of [M(CO)4(nbd)] (M = Cr or Mo;nbd = norbornadiene) toward (Ph2PN)C(Ph)[N(SiMe3)2] and C6H4{C[N(SiMe3)2]-(NPPh2)}2-1,4

Abstract

The interaction of (Ph 2 PN)C(Ph)[N(SiMe 3 ) 2 ] with 1 equivalent of [M(CO) 4 (nbd)] (M = Cr or Mo, nbd = norbornadiene) in diethyl ether gave cis-[M(CO) 4 {(Me 3 SiN)C(Ph)(NHPPh 2 }] (M = Cr 1 or Mo 2) in good yield. The interaction of C 6 H 4 {C(NPPh 2 )[N(SiMe 3 ) 2 ]} 2 -1,4 with 2 equivalents of [M(CO) 4 (nbd)] (M = Cr or Mo) in tetrahydrofuran gave the symmetric dimer cis-[{M(CO) 4 }{(Ph 2 PNH)(Me 3 SiN)CC 6 H 4 C(NSiMe 3 )(NHPPh 2 )}] (M = Cr 3 or Mo 4) in moderate yield. However, in diethyl ether, this reaction (M = Mo) gave the unsymmetric cis-[(OC) 4 Mo{(Ph 2 PNH)(Me 3 SiN)CC 6 H 4 C[N(SiMe 3 ) 2 ](NPPh 2 )}Mo(CO) 5 ] 5 in moderate yield. Compounds 1–5 have been fully characterized by analytical and spectroscopic methods and the structures of 3 and 5 have been established by X-ray crystallography. A 1,3-silyl shift mechanism has been proposed for the formation of the products. The NH proton of the bidentate iminophosphine ligand undergoes facile deuterium exchange with D 2 O at ambient temperature.