Premium
Reductive Activation of Tripod Cobalt Compounds: Oxidative Addition of H−H, P−H, and Sn−H Functions
Author(s) -
Winterhalter Ute,
Zsolnai Laszlo,
Kircher Peter,
Heinze Katja,
Huttner Gottfried
Publication year - 2001
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(20011)2001:1<89::aid-ejic89>3.0.co;2-2
Subject(s) - chemistry , tripod (photography) , reagent , yield (engineering) , cobalt , cyclic voltammetry , medicinal chemistry , oxidative addition , reductive elimination , argon , spectroscopy , nuclear magnetic resonance spectroscopy , photochemistry , stereochemistry , inorganic chemistry , organic chemistry , electrochemistry , catalysis , physics , materials science , electrode , optics , metallurgy , quantum mechanics
Treatment of the tripod compounds tripod CoCl 2 ( 1 ), and tripod CoCl ( 2 ), [ tripod = CH 3 C(CH 2 PPh 2 ) 3 ] in THF solution under argon atmosphere with strong reducing agents such as KC 8 leads to the generation of reactive species. While the dinitrogen compound tripod Co(N 2 )Co tripod ( 3 ), which is formed under N 2 atmosphere, is rather unreactive, the species formed under argon atmosphere undergo selective reactions with compounds containing P−H or Sn−H functions. With PhPH 2 as the reagent, the diphosphene compound tripod Co(η 2 ‐PhP=PPh) ( 8 ), is formed in a yield (44%) similar to that achieved in the preparation of 8 from 2 and PhPHNa (60%). With Ph 3 SnH as the reagent, tripod CoSnPh 3 ( 9 ), is obtained (yield 61%), while reaction with Bu 3 SnH produces tripod Co(H) 2 SnBu 3 ( 10a , 50%). The Co I species 9 undergoes oxidative addition of dihydrogen to produce the Co III compound tripod Co(H) 2 SnPh 3 ( 10b ), which is an analogue of 10a . The properties of these new compounds are characterized by the usual analytical techniques, including NMR spectroscopy, cyclic voltammetry, and X‐ray analysis.