Premium
Steric and Electronic Effects of Chelating Phosphines: Synthesis, Spectral, and Single Crystal X‐Ray Structural Studies on [1,3‐Bis(diphenylphosphino‐k,P,P′)propane](diisopropyldithiocarbamato)nickel(II) Perchlorate and [1,3‐Bis(diphenylphosphino‐k,P,P′)propane](piperidinecarbodithioato)nickel(II) Perchlorate
Author(s) -
Manohar A.,
Ramalingam K.,
Thiruneelakandan R.,
Bocelli G.,
Righi Lara
Publication year - 2001
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/1521-3749(200105)627:5<1103::aid-zaac1103>3.0.co;2-8
Subject(s) - steric effects , chemistry , perchlorate , nickel , phosphine , chromophore , crystal structure , metal , crystallography , electronic effect , stereochemistry , ion , chelation , pyridine , medicinal chemistry , inorganic chemistry , photochemistry , catalysis , organic chemistry
The complexes [Ni(dipdtc)(1,3‐dppp)]ClO 4 ( 1 ) and [Ni(pipdtc)(1,3‐dppp)]ClO 4 ( 2 ) (dipdtc – = diisopropyldithiocarbamate anion, pipdtc – = piperidinecarbodithioato anion, 1,3‐dppp = 1,3‐bis(diphenylphosphino)propane) have been prepared from the parent dithiocarbamato complexes with 1,3‐dppp in CH 3 CN–CH 3 OH and characterized by electronic and IR spectra and their structures are determined by X‐ray crystallography. The crystal structures of the complexes have planar NiS 2 P 2 chromophores. The complexes 1 and 2 are asymmetric with respect to their Ni–S and Ni–P distances. The P–Ni–P angles in both complexes, are larger than those observed in the diphenylphosphino ethane analogues. Thioureide νC–N bands occur at 1512 and 1536 cm –1 for compounds 1 and 2 respectively. The increased νC–N value is due to flow of electron density from nitrogen towards the metal ion. Electronic spectra show the signature bands at 460 for 1 and 450 nm for 2 .