+ Site Statistics
+ Search Articles
+ Subscribe to Site Feeds
Most Shared
PDF Full Text
+ PDF Full Text
Request PDF Full Text
+ Follow Us
Follow on Facebook
Follow on Twitter
Follow on LinkedIn
+ Translate
+ Recently Requested

Radical bonding: structure and stability of bis(phenalenyl) complexes of divalent metals from across the periodic table

Radical bonding: structure and stability of bis(phenalenyl) complexes of divalent metals from across the periodic table

Inorganic Chemistry 48(13): 5810-5819

We examine the bonding possibilities of the bis(phenalenyl) MP(2) sandwich complexes of the divalent metals M = Be, Mg, Ca, Sr, Ba, Zn, Cd, and Hg, at the B3LYP level of theory. The outcome is an extraordinarily diverse class of low symmetry bis(phenalenyl)metal complexes in which bonding preferences and binding enthalpies differ dramatically. The lowest energy group 2 metal MP(2) complexes include an intriguing eta(1),eta(3) BeP(2) structure, and bent eta(6),eta(6) systems for M = Ca, Sr, and Ba. The group 12 bis(phenalenyl) complexes are thermodynamically unstable eta(1),eta(1) slip-sandwich structures. To better understand changes in the structural preferences going from the (eta(6),eta(6)) group 2 to the (eta(1),eta(1)) group 12 complexes, we explored the bonding in the bis(phenalenyl) complexes of transition metals with stable +2 oxidations states between Ca and Zn in period 4. The computed binding enthalpies are large and negative for nearly all of the minimum energy bis(phenalenyl) complexes of the group 2 and the transition metals; they are tiny for MgP(2), and are quite positive for the group 12 systems. The structural preferences and stability of the complexes is a subtle negotiation of several influences: the (un)availability of (n - 1)d and np, orbitals for bonding, the cost of the rehybridization at carbon sites in the phenalenyl rings in preparation for bonding to the metals, and the (P---P) interaction between the phenalenyl radicals.

(PDF emailed within 0-6 h: $19.90)

Accession: 055345699

Download citation: RISBibTeXText

PMID: 19480444

DOI: 10.1021/ic900058q

Related references

Intermolecular pi-to-pi bonding between stacked aromatic dyads. Experimental and theoretical binding energies and near-IR optical transitions for phenalenyl radical/radical versus radical/cation dimerizations. Journal of the American Chemical Society 126(42): 13850-8, 2004

Radical hydrogen bonding: origin of stability of radical-molecule complexes. Journal of Chemical Physics 127(16): 164102, 2007

Complexes of thiocarbohydrazide with divalent metals: Stability constants in aqueous solutions. Inorganica Chimica Acta 3: 459-462, 1969

Stability Constants of Complexes of Divalent and Rare Earth Metals with Substituted Salicynals. Monatshefte für Chemie - Chemical Monthly 131(3): 267-276, 2000

Is there a lower limit to the CC bonding distances in neutral radical pi-dimers? The case of phenalenyl derivatives. Journal of the American Chemical Society 132(31): 10648-9, 2010

Superalkali atoms bonding to the phenalenyl radical: structures, intermolecular interaction and nonlinear optical properties. Journal of Molecular Modeling 21(8): 209, 2015

Theoretical analysis of intermolecular covalent pi-pi bonding and magnetic properties of phenalenyl and spiro-biphenalenyl radical pi-dimers. Journal of Physical Chemistry. a 111(28): 6304-6315, 2007

Hybrid density functional theory studies on the magnetic interactions and the weak covalent bonding for the phenalenyl radical dimeric pair. Journal of the American Chemical Society 124(37): 11122-11130, 2002

Synthesis and crystal structure of complexes of bipodal thiophosphorylated thioureas with divalent transition metals. Polyhedron 23(14): 2243-2252, 2004

Table salt and other alkali metal chloride oligomers: structure, stability, and bonding. Inorganic Chemistry 46(13): 5411-5418, 2007

Nickel(II)-phenoxyl radical complexes: structure-radical stability relationship. Inorganic Chemistry 43(24): 7816-7822, 2004

First-principles phase stability, bonding, and electronic structure of actinide metals. Journal of Electron Spectroscopy and Related Phenomena 194: 2-7, 2014

ESR and calculations on electronic structure of phenalenyl and phenalenyl derivative radicals. Magnetic Resonance in Chemistry 53(2): 99-102, 2014

Curve-structured phenalenyl chemistry: synthesis, electronic structure, and bowl-inversion barrier of a phenalenyl-fused corannulene anion. Journal of the American Chemical Society 130(45): 14954-5, 2008

Predicting the relative stability of simple versus ansa-sandwich systems across groups: structure, bonding, and (in)stability in tris(sandwich)benzene complexes. Chemistry 17(6): 1936-1945, 2011