Premium
Bis(phthalocyaninato(2–)rhenium(II)): Synthesis, Properties, and Crystal Structure
Author(s) -
Göldner Melanie,
Hückstädt Heiner,
Murray Keith S.,
Moubaraki Boujemaa,
Homborg Heiner
Publication year - 1998
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/(sici)1521-3749(199802)624:2<288::aid-zaac288>3.0.co;2-l
Subject(s) - rhenium , triclinic crystal system , triphenylphosphine , chemistry , crystallography , crystal structure , stereochemistry , inorganic chemistry , catalysis , biochemistry
Blue, paramagnetic bis(phthalocyaninato(2–)rhenium(II)) (μ eff = 0,88 μ B , per Re, at 300 K) is prepared by thermal decomposition of trans ‐bis(triphenylphosphine)phthalocyaninato(2–)rhenium(II), in boiling triphenylphosphine. It crystallizes in the triclinic space group P 1 with cell parameters as follows: a = 7.799(3) Å, b = 12.563(7) Å, c = 12.69(1) Å, α = 89.97(5)°, β = 94.14(5)°, γ = 106.39(4)°; Z = 1. Two cofacial phthalocyaninates are bonded together by a Re–Re bond with a Re–Re distance of 2.285(2) Å. The Re atoms are located distinctly outside the centre of the (N iso ) 4 planes by 0.426(3) Å. The Re–N iso distance varies from 1.99(1) to 2.04(1) Å (average 2.02 Å). The pc 2– ligands are in an eclipsed conformation and concavely distorted. In the UV‐VIS‐NIR spectrum the B region is split into two bands of comparable intensity due to strong excitonic coupling. The Re–Re stretching vibration at 240 cm –1 is selectively enhanced in the resonance Raman spectrum (λ exc = 488 nm).