Ligand control of agostic M ⋯ H ⋯ C three-centre, two-electron bonding in bicyclo[2.2.1]hept-2-yl complexes of platinum and palladium. X-Ray crystal structures of [Pt(η²-C₇H₁₀){Bu^t₂P(CH₂)₂PBu^t₂}] and [Pt(C₇H₁₁){Bu^t₂P(CH₂)₂PBu^t₂}][BPh₄]

The First Catalytic Synthesis of an Acrylate from CO2 and an Alkene—A Rational Approach

“…Mass spectra were recorded on a Finnigan LCQ with a quadrupole ion trap (positive ion channel). Bis(di-tert-butylphosphino)ethane [45] and bis(di-tert-butylphosphino)propane [46] were synthesized by following reported procedures. X-ray structures were solved by direct methods and refined against F 2 with a full-matrix least-squares algorithm by using the SHELXTL (Version 2008/4) software package- [47] Intensities were corrected for Lorentz and polarization effects.…”

True and masked three-coordinate T-shaped platinum(II) intermediates

“…7). Pioneering studies on alkyl complexes from Orpen’s and Spencer’s research groups reported the synthesis of cationic [Pt(norbornyl)(P–P)] + complexes A1a – e (P–P = bidentate phosphine ligand) [34–35]. Further studies involved other alkyl ligands such as ethyl ( A2b – c ), 3,3-dimethylbutyl ( A3b – c ) and 2,3,3-trimethylbutyl ( A4 ) [36–38].…”

“…Spencer et al reported that the formation of stable electron-deficient Pt(II) complexes stabilized by strong β-agostic interactions can be accessible by protonation of electron-rich alkene Pt(0) compounds 4 (Scheme 6) [35–36]. …”

“…As a representative example, Scheme 24 shows the β-H elimination for A1d together with the reverse 1,2-insertion for 56 . Interestingly, upon crystallization in dichloromethane solvent, A1d eliminates norbornene from 56 and generates the dinuclear complex 57 [35]. The presence of chloride as a bridging ligand suggests that solvent molecules are involved in the reaction.…”

“…β-H elimination and 1,2-insertion equilibrium involving A1d and the subsequent generation of 57 [35]. …”