A study of M-X-BR3 (M = Pt, Pd or Rh; X = Cl or I) interactions in square planar ambiphilic ligand complexes: structural, spectroscopic, electrochemical and computational comparisons with borane-free analogues.
Reaction of [PtCl(2)(COD)] and [PtI(2)(COD)] with 2,7-di-tert-butyl-5-diphenylboryl-4-diphenylphosphino-9,9-dimethylthioxanthene (TXPB) afforded square planar [PtCl(2)(TXPB)] (1B) and [PtI(2)(TXPB)] (4B), both of which were crystallographically characterized. Single-crystal X-ray quality crystals were also obtained for [PdCl(2)(TXPB)] (2B; Emslie et al., Organometallics, 2008, 27, 5317) as 2B·2CH(2)Cl(2) and solvent-free 2B. Both the chloro and iodo TXPB complexes exhibit metal-halide-borane bridging interactions similar to those in previously reported [RhCl(CO)(TXPB)] (3B) and [RhI(CO)(TXPB)] (5B) (Emslie et al., Organometallics, 2006, 25, 583 and Inorg. Chem., 2010, 49, 4060). To facilitate a more detailed analysis of M-X-BR(3) (X = Cl and I) interactions, a borane-free analogue of the TXPB ligand, 2,7-di-tert-butyl-4-diphenylphosphino-9,9-dimethylthioxanthene (TXPH), was prepared. Reaction with [PtX(2)(COD)] (X = Cl or I), [PdCl(2)(COD)] and 0.5 [{RhCl(CO)(2)}(2)] provided square planar [PtCl(2)(TXPH)] (1H), [PdCl(2)(TXPH)] (2H), [RhCl(CO)(TXPH)] (3H) and [PtI(2)(TXPH)] (4H). M-Cl-BR(3) and M-I-BR(3) bonding in 1B-5B was then probed through the use of structural comparisons, IR and NMR spectroscopy, cyclic voltammetry, and DFT calculations (Slater-type orbitals, Mayer bond orders, Hirshfeld charges, fragment analysis, SCF deformation density isosurfaces, and energy decomposition analysis).
Department of Chemistry, McMaster University, 1280 Main Street West, Hamilton, ON L8S 4M1, Canada. emslied@mcmaster.ca
David J H
DJ
Emslie
Bradley E
BE
Cowie
Simon R
SR
Oakley
Natalie L
NL
Huk
Hilary A
HA
Jenkins
Laura E
LE
Harrington
James F
JF
Britten