ic7b00027_si_002.cif (5.07 MB)

Cationic and Neutral Cp*M(NO)(κ2‑Ph2PCH2CH2PPh2) Complexes of Molybdenum and Tungsten: Lewis-Acid-Induced Intramolecular C–H Activation

Download (5.07 MB)
posted on 02.03.2017, 00:00 by Rex C. Handford, Russell J. Wakeham, Brian O. Patrick, Peter Legzdins
Treatment of CH2Cl2 solutions of Cp*M­(NO)­Cl2 (Cp* = η5-C5(CH3)5; M = Mo, W) first with 2 equiv of AgSbF6 in the presence of PhCN and then with 1 equiv of Ph2PCH2CH2PPh2 affords the yellow–orange salts [Cp*M­(NO)­(PhCN)­(κ2-Ph2PCH2CH2PPh2)]­(SbF6)2 in good yields (M = Mo, W). Reduction of [Cp*M­(NO)­(PhCN)­(κ2-Ph2PCH2CH2PPh2)]­(SbF6)2 with 2 equiv of Cp2Co in C6H6 at 80 °C produces the corresponding 18e neutral compounds, Cp*M­(NO)­(κ2-Ph2PCH2CH2PPh2) which have been isolated as analytically pure orange–red solids. The addition of 1 equiv of the Lewis acid, Sc­(OTf)3, to solutions of Cp*M­(NO)­(κ2-Ph2PCH2CH2PPh2) at room temperature results in the immediate formation of thermally stable Cp*M­(NO→Sc­(OTf)3)­(H)­(κ3-(C6H4)­PhPCH2CH2PPh2) complexes in which one of the phenyl substituents of the Ph2PCH2CH2PPh2 ligands has undergone intramolecular orthometalation. In a similar manner, addition of BF3 produces the analogous Cp*M­(NO→BF3)­(H)­(κ3-(C6H4)­PhPCH2CH2PPh2) complexes. In contrast, B­(C6F5)3 forms the 1:1 Lewis acid–base adducts, Cp*M­(NO→B­(C6F5)3)­(κ2-Ph2PCH2CH2PPh2) in CH2Cl2 at room temperature. Upon warming to 80 °C, Cp*Mo­(NO→B­(C6F5)3)­(κ2-Ph2PCH2CH2PPh2) converts cleanly to the orthometalated product Cp*Mo­(NO→B­(C6F5)3)­(H)­(κ3-(C6H4)­PhPCH2CH2PPh2), but Cp*W­(NO→B­(C6F5)3)­(κ2-Ph2PCH2CH2PPh2) generates a mixture of products whose identities remain to be ascertained. Attempts to extend this chemistry to include related Ph2PCH2PPh2 compounds have had only limited success. All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.