title: Electronic stabilization of trigonal bipyramidal clusters: the role of the Sn(II) ions in [Pt5(CO)5{Cl2Sn(μ-OR)SnCl2}3]3- (R = H, Me, Et, iPr).
abstract: The new [Pt(5)(CO)(5){Cl(2)Sn(μ-OR)SnCl(2)}(3)](3-) (R = H, Me, Et, (i)Pr; 1-4) clusters contain trigonal bipyramidal (TBP) Pt(5)(CO)(5) cores, as certified by the X-ray structures of [Na(CH(3)CN)(5)][NBu(4)](2)[1]·2CH(3)CN and [PPh(4)](3)[4]·3CH(3)COCH(3). The TBP geometry, which is rare for group 10 metals, is supported by an unprecedented interpenetration with a nonbonded trigonal prism of tin atoms. By capping all the Pt(3) faces, the Sn(II) lone pairs account for both Sn-Pt and Pt-Pt bonding, as indicated by DFT and topological wave function studies. In the TBP interactions, the metals use their vacant s and p orbitals using the electrons provided by Sn atoms, hence mimicking the electronic picture of main group analogues, which obey the Wade's rule. Other metal TBP clusters with the same total electron count (TEC) of 72 are different because the skeletal bonding is largely contributed by d-d interactions (e.g., [Os(5)(CO)(14)(PR(3))(μ-H)(n)](n-2), n = 0, 1, 2). In 1-4, fully occupied d shells at the Pt(ax) atoms exert a residual nucleophilicity toward the adjacent main group Sn(II) ions permitting their hypervalency through unsual metal donation.
authors.affiliation: Dipartimento di Chimica Inorganica, Metallorganica ed Analitica Lamberto Malatesta, Università degli Studi di Milano, via Venezian 21, 20133 Milano, Italy.
authors.forename: Alessandro
authors.initials: A
authors.lastname: Ceriotti
authors.forename: Matteo
authors.initials: M
authors.lastname: Daghetta
authors.forename: Simona
authors.initials: S
authors.lastname: El Afefey
authors.forename: Andrea
authors.initials: A
authors.lastname: Ienco
authors.forename: Giuliano
authors.initials: G
authors.lastname: Longoni
authors.forename: Gabriele
authors.initials: G
authors.lastname: Manca
authors.forename: Carlo
authors.initials: C
authors.lastname: Mealli
authors.forename: Stefano
authors.initials: S
authors.lastname: Zacchini
authors.forename: Salvatore
authors.initials: S
authors.lastname: Zarra