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Formation of η1-P-(2-Phosphinophenol)Ni(0)(PMe3)3 and Oxidation to cis/trans-Bis(2-phosphinophenolato)nickel(II) Complexes
-
Joachim Heinicke
,
Attila Dal
Veröffentlicht/Copyright:
2. Juni 2014
o-Phosphinophenols 1 (P⌒OH ) react with equimolar amounts of Ni(PMe3)4 at low temperatures to give yellow Ni(0) complexes such as [(HO∼P)Ni(PMe3)3] 2a with only P coordination of the P⌒OH ligand. Oxidation of solutions of 1 and Ni(PMe3)4 by dioxygen leads to brown bis(o-phosphinophenolato-P⌒O)nickel chelate complexes 3a-d. Structure elucidation by NMR is consistent with a cis-square planar geometry for 3a-c and a trans-square planar solution structure of the tert-butylphenylphosphino derivative 3d. The geometric isomers were distinguished by different ranges of phosphorus coordination shifts and 31P-13C-2 and 31P-13C-1 coupling constants. In the solid state, 3d adopts also a cis-square planar geometry. The steric stress of the substituents causes anti-orientation of the tert-butyl groups at phosphorus (R,R and S,S diastereoisomers) and a significant distorsion (22°) of the planes of the two five-membered rings. With less bulky substituents the R,S and S,R diastereoisomers are preferred as in the cis-square planar complex 3c with syn-orientation of the two isopropyl and phenyl groups, respectively.
Received: 1999-5-19
Published Online: 2014-6-2
Published in Print: 1999-10-1
© 1946 – 2014: Verlag der Zeitschrift für Naturforschung
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Schlagwörter für diesen Artikel
Phosphinophenolate;
Nickel;
Complexes;
Structure Elucidation;
Solid State Structures
Artikel in diesem Heft
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