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Transformations of Hydrazines RNHNH 2 (R = Me, Ph) at a Sulfur‐Rich Bimetallic Site: Diazene−Diazenido−Isodiazene/Hydrazido(2−) Interconversions
Author(s) -
Schollhammer Philippe,
Didier Béatrice,
Le Grand Nathalie,
Pétillon François Y.,
Talarmin Jean,
Muir Kenneth W.,
Teat Simon J.
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200203)2002:3<658::aid-ejic658>3.0.co;2-b
Subject(s) - chemistry , protonation , deprotonation , acetonitrile , bimetallic strip , nitrile , isomerization , sulfur , medicinal chemistry , nitrogen atom , nitrogen , photodissociation , polymer chemistry , organic chemistry , ion , ring (chemistry) , metal , catalysis
The bis(nitrile) compound [Mo 2 Cp 2 (µ‐SMe) 3 (MeCN) 2 ](BF 4 ) ( 1 ) (Cp = C 5 H 5 ) reacted with substituted hydrazines RNHNH 2 (R = Me, Ph) in acetonitrile at room temperature to give the stable diazene species [Mo 2 Cp 2 (µ‐SMe) 3 (μ‐η 2 ‐HN=NR)](BF 4 ) [R= Me ( 2 ), Ph ( 3 )]. Compounds 2 and 3 could be readily deprotonated with BuLi to produce neutral diazenido species [Mo 2 Cp 2 (µ‐SMe) 3 (µ‐η 2 ‐N=NR)] [R = Me ( 4 ), Ph ( 5 )]. Photolysis of 4 in THF induced isomerization of the diazenide bridge, affording the complex [Mo 2 Cp 2 (µ‐SMe) 3 (µ‐η 1 ‐N=NMe)] ( 8 ). This species underwent protonation at the outer nitrogen atom (N β ) to give the stable isodiazene/hydrazido(2−) complex [Mo 2 Cp 2 (µ‐SMe) 3 (μ‐η 1 ‐N=NHMe)](BF 4 ) ( 9 ) which isomerised slowly back into 2 on warming. The molecular structure of the µ‐η 2 ‐methyldiazenido complex 4 was established by an X‐ray diffraction study.