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Chelating Coordination of Di‐ and Triallylamines: Syntheses and NMR Studies of Trimethylphosphane Nickel and Cobalt Complexes
Author(s) -
Klein HansFriedrich,
Helwig Michael,
Braun Siegmar
Publication year - 1994
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19941270903
Subject(s) - chemistry , cobalt , nickel , tetrahydrofuran , chelation , allylic rearrangement , medicinal chemistry , coordination complex , yield (engineering) , stereochemistry , nmr spectra database , proton nmr , olefin fiber , metal , inorganic chemistry , catalysis , spectral line , organic chemistry , materials science , physics , astronomy , solvent , metallurgy
16‐Electron complexes of zerovalent nickel with diallylamines, Ni[(C 3 H 5 ) 2 NR]L [ 1 , 2 : L = P(CH 3 ) 3 , R = CH 3 , C 6 H 5 ; 3 : L = P(C 6 H 5 ) 3 , R = CH 3 ] and [NiP(CH 3 ) 3 ] 2 CH 2 [N(C 3 H 5 ) 2 ] 2 ( 4 ), were synthesized by reduction of NiCl 2 L 2 with magnesium in tetrahydrofuran. NiCl(η 3 ‐C 3 H 5 )[P(CH 3 ) 3 ] 2 ( 5 ), a low‐yield byproduct, was also obtained in high yield from NiL 4 and C 3 H 5 Cl. With triallylamine as starting material complexes Ni[(C 3 H 5 ) 3 N]L [ 6 : L = P(CH 3 ) 3 ; 7 : L = P(C 6 H 5 ) 3 ] were generated exhibiting η 6 ‐ and η 4 ‐olefin coordination, respectively. 17‐electron cobalt(O) compounds Co[(C 3 H 5 ) 2 NR](PMe 3 ) 2 ( 8 , 9 : R = CH 3 , C 6 H 5 ) were obtained by reaction of Co( cyclo ‐C 5 H 8 )(PMe 3 ) 3 with the corresponding diallylamine, while CoR(PMe 3 ) 4 (R = CH 3 , C 6 H 5 ) reacted with N,N ‐diallylaniline to give diagmagnetic Co[(η 3 ‐C 3 H 4 )(η 2 ‐C 3 H 5 )NC 6 H 5 ](PMe 3 ) 2 , ( 10 ). The coordination mode of allylic functions was deduced from IR, ESR and especially 1 H‐ and 13 C‐NMR spectra including 2D‐NMR experiments.