191657-83-7Relevant academic research and scientific papers
Reactions of tungsten(VI) dialkyl complexes with tBuNC: Synthesis and characterization of new square pyramidal and trigonal bipyramidal tungsten (VI) complexes
Huff, R. Leigh,Wang, Shu-Yu S.,Abboud, Khalil A.,Boncella, James M.
, p. 1779 - 1785 (1997)
The complexes [(TMS)2pda](NPh)WR2 ((TMS)2pda = o-(Me3SiN)2C6H4}2-; R = CH3 (1), CH2-CMe3 (4)) react with tBuNC to form the octahedral monoadducts [(TMS)2pda](NPh)WR2(CNt-Bu) (Ia and 4a). Ia is observed only at low temperature, while 4a can be isolated. Both Ia and 4a react with tBuNC to form the corresponding trigonal bipyramidal bis(η2-imino-acyl) species [(TMS)2pda](NPh)W[η2-(tBu)NCR]2 (R = CH3 (2), CH2CMe3 (5)), which have been isolated and characterized. Compound 2 isomerizes upon heating to the square pyramidal metallacycle [(TMS)2pda](NPh)W[(tBu)NC(CH3)=C(CH 3)N(tBu)] (3), which has been isolated as a red solid. X-ray crystal structures have been obtained for compounds 2 and 3. Crystals of 2 are orthorhombic, space group P212121, with α= 9.1175(3) A?, b = 17.9587(5) A?, c = 20.9435(6) A?, and Z = 4. Compound 2 has trigonal bipyramidal geometry with the imido N and one amido N in axial positions. Crystals of 3 are monoclinic, space group C2/c, with α = 35.1302(9) A?, b = 12.6459(2) A?, c = 16.2386(6) A?, β= 112.021(3)°, and Z = 8. 3 has distorted square pyramidal geometry with the imido moiety in the apical position.
