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Experimental and Computational Study on a Variety of Structural Motifs and Coordination Modes in Aluminium Complexes of Di(2‐pyridyl)amides and ‐phosphanides
Author(s) -
Pfeiffer Matthias,
Murso Alexander,
Mahalakshmi Lepakshaiah,
Moigno Damien,
Kiefer Wolfgang,
Stalke Dietmar
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(200212)2002:12<3222::aid-ejic3222>3.0.co;2-u
Subject(s) - chemistry , amide , ligand (biochemistry) , aluminium , stereochemistry , acceptor , coordination complex , ion , crystallography , metal , receptor , organic chemistry , biochemistry , physics , condensed matter physics
The (2‐Py) 2 N − ligand shows much more conformational freedom than the (2‐Py) 2 P − anion in aluminium coordination. The two isomers [Al{(NPy)Py} 3 ] ( 1a ) and [Al{(NPy)Py} 2 (Py 2 N)] ( 1b ) were isolated, the former containing exclusively cis ‐ trans ligands, and the latter cis ‐ trans ligands together with a trans ‐ trans ligand. The energy differences in the noncoordinated anions (2‐Py) 2 E − (E = N, P) were determined by computational methods to be low in the amide. While the N⇄Al donor bond energy is appreciable (96 kJ/mol), that of the P⇄Al donor bond is much lower (45 kJ/mol). This explains why the P‐analogous donor‐acceptor complex to Et 2 Al (2‐Py) 2 N⇄AlEt 3 could never be isolated. The P‐centred systems are much better π‐donors to soft metals than σ‐donors to hard metals. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)