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Atom‐ and Group Transfers to M IV Oxo and Imido Complexes, (η 5 ‐C 5 Me 5 )M[N( i Pr)C(Me)N( i Pr)](E) (M = Mo, W; E = O, NSiMe 3 ): Orthogonal Generation of a M VI Terminal Nitride via Inter‐ligand Silyl Group Migration
Author(s) -
Yonke Brendan L.,
Reeds Jonathan P.,
Zavalij Peter Y.,
Sita Lawrence R.
Publication year - 2015
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201400182
Subject(s) - chemistry , nucleophile , ligand (biochemistry) , cationic polymerization , nitrene , stereochemistry , medicinal chemistry , group (periodic table) , oxygen atom , nitride , crystallography , molecule , catalysis , polymer chemistry , organic chemistry , biochemistry , receptor , layer (electronics)
The group 6 M IV terminal oxo complexes, Cp*M[N( i Pr)C(Me)N( i Pr)](O) (Cp* = η 5 ‐C 5 Me 5 ) where M = Mo ( 1 ) and W ( 2 ) react with N 3 SiMe 3 to provide the M VI terminal nitrido complexes, Cp*M[N( i Pr)C(Me)N( i Pr)](N)(OSiMe 3 ) where M = Mo ( 5 ) and W ( 7 ), respectively. A mechanism involving nitrene group transfer to generate a M VI oxo, imido intermediate, followed by inter‐ligand silyl group transfer is proposed to account for formation of 5 and 7 . Compound 7 was alternatively prepared through an orthogonal route to the same proposed intermediate involving oxygen atom transfer from N 2 O to the W IV terminal imido complex Cp*W[N( i Pr)C(Me)N( i Pr)](NSiMe 3 ) ( 4 ). The nucleophilicity of the terminal nitride 7 was further established through methylation to provide cationic {Cp*W[N( i Pr)C(Me)N( i Pr)](NMe)(OSiMe 3 )}{I} ( 8 ).