357225-59-3Relevant academic research and scientific papers
The syntheses, structures and reactivity of bis(tert-butylcyclopentadienyl)molybdenum derivatives: nitrogen alkylation of an η2-acetonitrile ligand and influence of the chalcogen on the barrier to inversion of chalcogenoether adducts
Shin, Jun Ho,Savage, William,Murphy, Vincent J.,Bonanno, Jeffrey B.,Churchill, David G.,Parkin, Gerard
, p. 1732 - 1753 (2007/10/03)
An investigation of the chemistry of the tert-butyl-substituted molybdenocene system, {(Cpt-Bu)2Mo} (Cpt-Bu=C5H4But), has demonstrated that the η2-acetonitrile ligand in (Cpt-Bu)2Mo(η2-MeCN) may be alkylated by RI (R=Me, Et) at nitrogen to give iminoacyl derivatives, [(Cpt-Bu)2Mo(η2-MeC=NR)]-, which is a new type of reactivity for mononuclear acetonitrile complexes. A series of chalcogenolate-hydride complexes (Cpt-Bu)2Mo(EPh)H (E=S, Se, Te) have been obtained by reaction of (Cpt-Bu)2MoH2 with Ph2E2, and may be alkylated by MeI to give the chalcogenoether adducts [(Cpt-Bu)2Mo(PhEMe)H]I. Dynamic NMR studies on [(Cpt-Bu)2Mo(PhEMe)H]+ indicate that the barrier to inversion at the chalcogen increases in the sequence St-Bu)2MoO reacts with 2 equivalents of Me3SiX (X=Cl, Br, I, O2CMe, O3SMe) to yield (Cpt-Bu)2MoX2; for X=CN and NCS, (Cpt-Bu)2Mo(OSiMe3)X, the product of reaction with 1 equivalent may be isolated. (Cpt-Bu)2Mo(OSiMe3)X (X=CN, NCS) reacts with Me3SiNCS to give the thiocyanate complex (Cpt-Bu)2Mo(SCN)X, rather than the isocyanate isomer, (Cpt-Bu)2Mo(NCS)X, thereby indicating that the reactions do not involve a simple metathesis of the Si-NCS bond. Other complexes that are reported include: (Cpt-Bu)2MoX2 (X=H, Cl, Br, I, Me, CH2Ph, CH2SiMe3), (Cpt-Bu)2MoL (L=CO, C2H4, C2H2, MeCN, PMe3), [(Cpt-Bu)2Mo(μ-E)]2, (Cpt-Bu)2Mo(η2-E2) and (Cpt-Bu)2Mo(EPh)2 (E=S, Se, Te).
