Abstract
The reactions of the bromocarbyne complex [Mo(≡CBr)(CO) 2[HB(pzMe2)3}] (pz = pyrazol-1-yl) with a range of secondary and heterocyclic amines have been investigated and found in each case to proceed via simple nucleophilic halide substitution to provide N-functionalized carbyne derivatives, some of which are not available via conventional approaches. With diethylamine or piperazine the simple dialkyaminocarbyne complexes [Mo(≡CNEt2)(CO)2 {HB(pzMe2)3}] or [Mo {≡CN(C2H 4)2NH} (CO)2 [HB(pzMe2) 3]] were obtained. With 4-N,N-dimethylaminopyridine the pyridiniumcarbyne salt [Mo(≡CNC5H4NMe 2-4)-(CO)2[HB(pzMe2)3}]Br was obtained; pyridine provided a complex intractable mixture and collidine failed to react. N-Methylimidazole provided the imidazolium derivative [Mo(≡CNC3H3NMe)-(CO)2[HB(pzMe 2)3]]Br, while N-(trimethylsilyl)imidazole gave the neutral imidazolyl derivative [Mo(≡CNC3H3N)(CO) 2[HB(pzMe2)3)] and N,N′- bis(trimethylsilyl)imidazolium bromide. The sulfanamide HN(SPh)2 afforded the thiolatocarbyne complex [Mo(≡CSPh)(CO)2 {HB (pzMe2)3}] rather than the expected aminocarbyne complex [Mo{≡CN(SPh)2](CO)2[HB(pzMe2) 3}], while HN(PPh2S)2 failed to react. The complex 1 is unreactive toward 1,8-diazabicycloundecene (DBU); however prolonged heating results in the formation of [DBUH] [Mo(O)3 {HB (pzMe 2)3}] via base-induced hydrolysis/oxidation.
Original language | English |
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Pages (from-to) | 4532-4540 |
Number of pages | 9 |
Journal | Organometallics |
Volume | 27 |
Issue number | 17 |
DOIs | |
Publication status | Published - 8 Sept 2008 |