Synthesis of α-functionalised-alkylplatinum(II) complexes by oxidative addition of geminal dihalides to platinum(0) substrates; X-ray structure of cis-[Pt(CH₂I)I(PPh₃)₂]

Facile Oxidative Addition of Organic Halides to Heteroleptic and Homoleptic Pd0–N‐Heterocyclic Carbene Complexes

“…The imidazoline ring is significantly twisted from the two 2,6-bis(isopropyl)phenyl rings with the dihedral angle of 73.54 (6) [25] which was prepared from [PdCl 2 (cod)] (cod = 1,2-cyclooctadiene), excess amounts of diazomethane or bis(chloromethyl)mercury, followed by the ligand replacement with PPh 3 . Although many cases of the thermal or photoinduced oxidative addition of dihalomethanes to low-valent Pt, [27][28][29][30] Pd, [24,[31][32][33] Rh, [34][35][36][37][38][39][40][41][42][43] Ru, [44] Ir, [45][46][47] Co, [48] and Au [49] complexes were reported, only a few cases have been known to date for zero-valent Pd complexes, including [Pd(PtBu 2 -H) 3 ], [24] [Pd(PCy 3 ) 2 (dba)] (dba = dibenzylideneacetone; Cy = cyclohexyl), [31] and [PdN(CH 2 CH 2 PPh 2 ) 3 ]. [28] Furthermore, there have been no reports for the structural characterization of the oxidative addition complex Cl-PdCH 2 Cl by X-ray diffraction.…”

Oxidative Addition of Carbon−Chloride Bonds to Rhodium(I) Complexes Containing Terdentate Nitrogen Ligands. X-ray Analyses of Rhodium(I) Chloride and Rhodium(III) Chloromethyl Complexes

“…This is evidenced by the oxidative addition of CH 2 I 2 to [RhCp * (CO) 2 ] (Cp * = pentamethylcyclopentadiene), affording [RhI(CH 2 I)Cp * (CO)], while [RhCp(CO) 2 ] (Cp = cyclopentadiene) in contrast does not react, owing to the smaller electron donor capacity of Cp compared to Cp * − For example, reaction of [Rh(dmpe) 2 ]Cl containing the strongly electron donating Me 2 P(CH 2 ) 2 PMe 2 (dmpe) ligands with CH 2 Cl 2 afforded the complex [RhCl(CH 2 Cl)(dmpe) 2 ]Cl·CH 2 Cl 2 …”

Formation and Structure of a Platinum(II) Complex Containing TwotransNonstabilized Phosphorus Ylide Ligands: Evidence for Reversible Ylide Dissociation

“…22 Also, the complex trans-[PtI(CH 2 PEt 3 )-(PEt 3 ) 2 ] + I − was obtained by reacting Pt(PEt 3 ) 3 and CH 2 I 2 , presumably via the intermediate oxidative addition product PtI(CH 2 I)(PEt 3 ) 2 , which is further attacked by the released PEt 3 . 23 A possible reason for this unprecedented reactivity is related to the different coordination sphere and electronic environment around the Pt II center relative to those in previous studies, which generally involved neutral complexes with phosphine ligands. Once the first halide ligand is replaced to generate a cationic [Pt(ylide)X(PR 3 ) 2 ] + complex, there is a choice between substitution of the second halide ligand or deprotonation at the α-CH position of the already coordinated ylide ligand (see Scheme 2, L = PR 3 ).…”

“…Platinum(II) complexes with neutral, nonstabilized ylide ligands have previously been obtained by addition of the phosphine to a halomethyl precursor: for instance, the addition of excess PPh 3 to cis- Pt(COD)(CH 2 I) 2 yielded cis -[PtI(PPh 3 ) 2 (CH 2 PPh 3 ) 2 ] + I – , which was structurally characterized by X-ray diffraction . Also, the complex trans- [PtI(CH 2 PEt 3 )(PEt 3 ) 2 ] + I – was obtained by reacting Pt(PEt 3 ) 3 and CH 2 I 2 , presumably via the intermediate oxidative addition product PtI(CH 2 I)(PEt 3 ) 2 , which is further attacked by the released PEt 3 …”