Premium
Cobalt(I) and Nickel(II) Complexes of Bis(1,3‐diphosphacyclobutadiene) Sandwich Anions
Author(s) -
Rödl Christian,
Wolf Robert
Publication year - 2016
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.201500583
Subject(s) - chemistry , cobalt , nickel , cyclic voltammetry , cyclopentadienyl complex , crystallography , density functional theory , redox , ion , nuclear magnetic resonance spectroscopy , metal , stereochemistry , inorganic chemistry , medicinal chemistry , electrochemistry , computational chemistry , catalysis , electrode , organic chemistry
Complexes [(C 4 Me 4 )Co(CO) 2 {Co(P 2 C 2 t Bu 2 ) 2 }] ( 1 , C 4 Me 4 = tetramethylcyclobutadiene) and [CpNi{Co(P 2 C 2 t Bu 2 ) 2 }(PPh 3 )] ( 2 , Cp = cyclopentadienyl) were synthesized by transmetalating [Tl(thf) 2 {Co(P 2 C 2 t Bu 2 ) 2 }] with [(C 4 Me 4 )Co(CO) 2 I] and [CpNiBr(PPh 3 )]. Compounds 1 and 2 were fully characterized by X‐ray crystallography, multinuclear NMR, UV/Vis, and IR spectroscopy, and elemental analysis. Their molecular structures show σ‐coordination of one phosphorus atom of the [Co(P 2 C 2 t Bu 2 ) 2 ] – anion to the second metal atom (cobalt or nickel). Time‐dependent density functional theory (TD‐DFT) calculations were applied to gain insight into the electronic structures and the nature of the electronic transitions observed in the UV/Vis spectra. Cyclic voltammetry studies revealed the similar redox behavior of 1 and 2 , which are reversibly oxidized to the corresponding monocations 1 + and 2 + with retention of the dinuclear structures. The cyclic voltammograms furthermore show that 1 and 2 decompose upon reduction with cleavage of the dinuclear structures into the free [Co(P 2 C 2 t Bu 2 ) 2 ] – anion and further uncharacterized products.