Premium
P 4 Activation at Ni 0 : Selective Formation of an NHC‐Stabilized, Dinuclear Nickel Complex [Ni 2 ( i Pr 2 Im) 4 (μ,η 2:2 ‐P 2 )]
Author(s) -
Zarzycki Bartosz,
Zell Thomas,
Schmidt David,
Radius Udo
Publication year - 2013
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/ejic.201201368
Subject(s) - chemistry , nickel , crystallography , white phosphorus , planarity testing , dihedral angle , bent molecular geometry , metal , stereochemistry , molecule , phosphorus , hydrogen bond , organic chemistry
The reaction of [Ni 2 ( i Pr 2 Im) 4 (cod)] ( 1 ) with white phosphorus led to dinuclear [{Ni( i Pr 2 Im) 2 } 2 (μ,η 2:2 ‐P 2 )] ( 2 ) in excellent yield. This reaction represents the first example of a conversion of white phosphorus into a complex of the type [{L 2 Ni} 2 (μ,η 2:2 ‐P 2 )] and the first example of the formation of a complex of the type [{L 2 M} 2 (μ,η 2:2 ‐P 2 )] for a group‐10 metal stabilized by two simple, nonchelating, two‐electron donor ligands by the reaction of a suitable precursor with P 4 . The X‐ray structure of 2 revealed a bent Ni 2 P 2 core with an Ni–P–P–Ni dihedral angle in the solid state of 102.95°. According to DFT calculations on the symmetrized model systems planar ‐ D 2 h ‐ and bent ‐ C 2 v ‐[{Ni( i Pr 2 Im) 2 } 2 (μ,η 2:2 ‐P 2 )], this deviation of the Ni 2 P 2 core from planarity is caused by a second‐order Jahn–Teller distortion. Calculations on the related platinum compound [{Pt( i Pr 2 Im) 2 } 2 (μ,η 2:2 ‐P 2 )] confirmed this type of bent structure for the higher congener with an even higher barrier to planarization than that calculated for the nickel complex. Energy decomposition analysis and fragment molecular orbital analysis further illustrate the bonding mechanisms in these complexes.