Title: Reactions of Tungsten(VI) Dialkyl Complexes with <sup>t</sup>BuNC: Synthesis and Characterization of New Square Pyramidal and Trigonal Bipyramidal Tungsten(VI) Complexes
Abstract: The complexes [(TMS)2pda](NPh)WR2 ((TMS)2pda = o-(Me3SiN)2C6H4}2-; R = CH3 (1), CH2CMe3 (4)) react with tBuNC to form the octahedral monoadducts [(TMS)2pda](NPh)WR2(CNtBu) (1a and 4a). 1a is observed only at low temperature, while 4a can be isolated. Both 1a 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(CH3)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 a = 9.1175(3) Å, b = 17.9587(5) Å, c = 20.9435(6) Å, 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 a = 35.1302(9) Å, b = 12.6459(2) Å, c = 16.2386(6) Å, β = 112.021(3)°, and Z = 8. 3 has distorted square pyramidal geometry with the imido moiety in the apical position.
Publication Year: 1997
Publication Date: 1997-04-01
Language: en
Type: article
Indexed In: ['crossref']
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Cited By Count: 28
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