A Planar Ti2 P2 Core Assembled by Reductive Decarbonylation of - O-C≡P and P-P Radical Coupling

Lauren N Grant; Balazs Pinter; Brian C Manor; Riccardo Suter; Hansjörg Grützmacher; Daniel J Mindiola

doi:10.1002/chem.201701054

A Planar Ti₂ P₂ Core Assembled by Reductive Decarbonylation of ^- O-C≡P and P-P Radical Coupling

Chemistry. 2017 May 5;23(26):6272-6276. doi: 10.1002/chem.201701054. Epub 2017 Apr 21.

Authors

Lauren N Grant¹, Balazs Pinter², Brian C Manor¹, Riccardo Suter³, Hansjörg Grützmacher³, Daniel J Mindiola¹

Affiliations

¹ Department of Chemistry, University of Pennsylvania, Philadelphia, PA, 19104, USA.
² Eenheid Algemene Chemie (ALGC), Vrije Universiteit Brussel (VUB), Pleinlaan 2, 1050, Brussels, Belgium.
³ Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog Weg1, Hönggerberg, 8093, Zürich, Switzerland.

PMID: 28297126
DOI: 10.1002/chem.201701054

Abstract

The complex [(nacnac)Ti(OAr)]₂ (μ₂ :η² ,η² -P₂ ) (1) is formed via reductive decarbonylation of the phosphaethynolate ion ^- [OCP], which serves as a P atom source. Complex 1 is the first structurally characterized Group 4 transition metal P₂ complex and its structure reveals the rhombic Ti₂ P₂ core is essentially planar with short bond lengths suggesting some degree of multiple bonding character between the Ti-P and P-P sites. Computational studies of 1 provide an understanding of the Ti₂ P₂ core as well as the origin of the highly downfield ³¹ P NMR spectroscopic signal.

Keywords: P2; P4; aryloxide; phosphaethynolate; phosphorus; titanium.