title: The tipping point of the inert pair effect: experimental and computational comparison of In(I) and Sn(II) bis(imino)pyridine complexes.
abstract: The autoionization reaction of neutral bis(imino)pyridine and SnX2 led to three compounds [{ArN[double bond, length as m-dash]CPh}2(NC5H3)]SnX(+)SnX3(-) (Ar = 2,6-(2,5-(t)Bu2C6H3), X = Cl, Br; Ar = 2,6-(2,6-Me2C6H3), X = Cl) which display, within the same species, cations and anions possessing Sn(ii) centers. Computational analysis compared the ligated Sn(ii) cations with bis(imino)pyridine In(i) complexes that showed unprecedented weak metal-ligand covalent interactions, consistent with the In(i) 5s(2) electrons remaining as an inert nonbonding pair. Analysis of the metal-ligand bonding indicates that the chloride ligand of the Sn(ii) complex induces promotion of the metal 5s(2) electron pair to a stereochemically active hybridized orbital, which, in turn, allows strong coordination of the bis(imino)pyridine to Sn.
authors.affiliation: Department of Chemistry and the Centre for Catalysis Research and Innovation, University of Ottawa, Ottawa, ON, Canada. darrin@uottawa.ca.
authors.forename: Titel
authors.initials: T
authors.lastname: Jurca
authors.affiliation: Department of Chemistry, Memorial University of Newfoundland, St. John's, NL, Canada.
authors.forename: Lana K
authors.initials: LK
authors.lastname: Hiscock
authors.affiliation: Department of Chemistry and the Centre for Catalysis Research and Innovation, University of Ottawa, Ottawa, ON, Canada. darrin@uottawa.ca.
authors.forename: Ilia
authors.initials: I
authors.lastname: Korobkov
authors.affiliation: Department of Chemistry, Memorial University of Newfoundland, St. John's, NL, Canada.
authors.forename: Christopher N
authors.initials: CN
authors.lastname: Rowley
authors.affiliation: Department of Chemistry and the Centre for Catalysis Research and Innovation, University of Ottawa, Ottawa, ON, Canada. darrin@uottawa.ca.
authors.forename: Darrin S
authors.initials: DS
authors.lastname: Richeson