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Organometallic Complexes of Multianionic Phosphazenates
Author(s) -
Lawson Gavin T.,
Jacob Chacko,
Steiner Alexander
Publication year - 1999
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/(sici)1099-0682(199911)1999:11<1881::aid-ejic1881>3.0.co;2-9
Subject(s) - chemistry , diethylzinc , deprotonation , protonation , denticity , ring (chemistry) , medicinal chemistry , metal , polymer chemistry , inorganic chemistry , stereochemistry , organic chemistry , ion , enantioselective synthesis , catalysis
The amino‐substituted phosphazene P 3 N 3 (NHCy) 6 1 reacts as a multiprotic acid undergoing full deprotonation in the presence of Me 3 Al and Et 2 Zn, respectively, which results in the formation of multinuclear metal phosphazenates: Trimethyl aluminium deprotonates 1 with evolution of six equivalents of methane to give the pentanuclear organoaluminium complex [(thfMeAl)(Me 2 Al) 4 {P 3 N 3 (NCy) 6 }] 2 . Diethylzinc deprotonates 1 yielding the hexanuclear zinc complex [(EtZn) 6 {P 3 N 3 (NCy) 6 }] 3 . The higher homologue P 4 N 4 (NHCy) 8 4 reacts with diethylzinc undergoing sixfold deprotonation giving the hexanuclear complex [(EtZn) 6 {P 4 N 4 (NHCy) 2 (NCy) 6 }] 5 , where two NH functions remain protonated. All three metal complexes 2 , 3 and 5 are soluble in aprotic organic solvents. The highly charged phosphazenate ligands contain three and four PN 4 tetrahedra which are fused in a corner‐sharing manner forming P 3 N 3 and P 4 N 4 ring structures, respectively. These are isoelectronic with meta ‐silicate anions, but in addition equiped with organic groups at terminally arranged N atoms. Both phosphazenate ligands contain various coordination sites and show a high flexibility of their central P–N ring conformation toward the complexed organometallic framework.