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Lithium Oligophosphanediides in the Li/PhPCl 2 System
Author(s) -
Stein Daniel,
Dransfeld Alk,
Flock Michaela,
Rüegger Heinz,
Grützmacher Hansjörg
Publication year - 2006
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.200600571
Subject(s) - chemistry , lithium (medication) , ion , crystallography , sodium , inorganic chemistry , diffraction , organic chemistry , medicine , physics , optics , endocrinology
Optimized conditions for the selective synthesis of [Li 2 (P n Ph n )(tmeda) x ] ( n = 2, 3, 4) have been developed. X‐ray diffraction with single crystals show [Li 2 (P 2 Ph 2 )(tmeda) 2 ] and [Li 2 (P 4 Ph 4 )(tmeda) 2 ] to be ion triples, while for n = 3 the ion pair [Li(tmeda) 2 ] + [Li(P 3 Ph 3 )(tmeda)] – is observed. NMR experiments support the assumption that these structures are retained in solution. Structural differences between the lithium and the corresponding sodium compounds, [Na 2 (P n Ph n )(tmeda) x ], can be partially rationalized using the electrostatic stabilization parameters, ESP = Σ(1/ r M + ,M +) + Σ(1/ r P – ,P –) – Σ(1/ r M + ,P –); M = Li, Na. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)