Enhanced Relative Stability of Metallabenzenes versus Metallocenes upon Ring Perfluorination: Nickel, Palladium, and Platinum Systems. Issue 40 (16th October 2017)

• Record Type: Journal Article
• Authors: Li, Jing; Li, Guoliang; Xie, Yaoming; King, R. Bruce; Schaefer, Henry F.
• Is Part Of: European journal of inorganic chemistry. Issue 40(2017)
• Page Start: 4714
• Page End: 4721
• Publication Date: 2017-10-16
• Subjects: Metallocenes -- Metallabenzenes -- Density functional calculations -- Group‐10 metals -- Transition metals; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201700810
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Perfluorination of one η 5 ‐C5 H5 ring in the MC10 H10 system (M = Ni, Pd, Pt) to give an MC10 H5 F5 system greatly destabilizes structures containing a perfluorinated pentahapto η 5 ‐C5 F5 ring. As a result, the metallapentafluorobenzene structures (η 5 ‐C5 H5 )(MC5 F5 ) are the lowest‐energy structures for all three metals, with energy differences of 1.4, 6.2, and 16.2 kcal/mol for nickel, palladium, and platinum, respectively. In addition, palladium and platinum isomeric metallatetrafluorocyclopentadiene structures, with a complexed fluorobenzene ring; that is, (C6 H5 F)(MC4 F4 ) (M = Pd, Pt), are lower‐energy structures than the lowest‐energy metallocene structures. Furthermore, for palladium and platinum, the lowest‐energy metallocene structures are slipped metallocenes with a trihapto, rather than a pentahapto, pentafluorocyclopentadienyl ring. These theoretical results suggest the pentafluorocyclopentadienyl anion as a reagent for synthesizing metallapentafluorobenzene derivatives by reactions with (η 5 ‐C5 R5 )M(CO)X, (η 5 ‐C5 R5 )2 M2 (µ‐CO)2, or (η 5 ‐C5 R5 )2 Ni (R = H, Me; M = Ni, Pt). Abstract : Perfluorination of one η 5 ‐C5 H5 ring in the MC10 H10 system (M = Ni, Pd, Pt) to give an MC10 H5 F5 system greatly destabilizes structures containing a perfluorinated pentahapto η 5 ‐C5 F5 ring. As a result, the metallapentafluorobenzene isomers are the lowest‐energy structures for all three metals.