Synthesis, Characterisation and Hydrogen Bonding of Isostructural Group 10 Metal Halido Complexes Bearing a POCOP Ligand

Abstract

An isostructural series of nickel, palladium and platinum halido complexes of the type [(POCOP)MX] [POCOP = κ 3 -C 5 H 3 -2,6-(OPtBu 2 ) 2 ; X = F, Cl, I] was prepared and fully characterised. Molecular structures of complexes 1-I, 2-I, 3-Cl and 3-I are reported and show the typical distorted square-planar coordination geometries. In the presence of HF, Ni and Pt fluorido [a] Scheme 3. Synthesis of complex 2-Cl. Scheme 4. Synthesis of complexes 2-I and 2-F from 2-Cl.

Intermolecular hydrogen bonding in isostructural pincer complexes [OH-( t-BuPOCOP t-Bu)MCl] (M = Pd and Pt)

“…The M-Cl [1: 2.3871 (4), 2: 2.3907 (5) Å ] and M-P bonds [1: 2.2880 (3), 2.2918 (3); 2: 2.2781 (5), 2.2796 (5) Å ] are in the expected ranges and are in line with values found in previous examples for Pd and Pt PCP pincer complexes (e.g. Bolliger et al, 2007;Joksch et al, 2017Joksch et al, , 2018. As can be seen from the structural data, variation of the metal centre does not affect the structural features of the pincer complex.…”

“…A search of the Cambridge Structural Database (CSD, Version 5.40, May 2019 update;Groom et al, 2016) for Pd and Pt POCOP halide complexes with aromatic ligand backbones resulted in 58 hits. Similar Pd and Pt pincer complexes without the OH group in the 4-position have been reported by our group (Joksch et al, 2017(Joksch et al, , 2018. Related complexes have been described, e.g.…”

Fluorination Reactions at a Platinum Carbene Complex: Reaction Routes to SF3, S(=O)F and Fluorido Complexes

“…Removal of the solvent from the product solution under reduced pressure afforded the bifluorido complex trans ‐[Pt(H)(FHF)(IMes) 2 ] ( 8 ). Transition metal complexes with hydrido bifluorido ligands are described in the literature and often result from reaction of the corresponding hydrido compounds with an excess HF or coordination of HF at fluorido ligands [1j,3b,5d,6b,9a,27] . A subsequent conversion of 8 into the fluorido complex trans ‐[Pt(H)(F)(IMes) 2 ] ( 4 ) was successful by removal of HF from the ligand sphere by addition of CsF to a solution of 8 in C 6 H 6 (Scheme 3).…”

Platinum thiolate complexes supported by PBP and POCOP pincer ligands as efficient catalysts for the hydrosilylation of carbonyl compounds

“…Again, complexes 1a and 1b are more active than complexes 2a and 2b (entries 14 and 15 vs. entries 16 and 17). Although these platinum complexes are also active in catalysing the hydrosilylation of 4-chlorobenzophenone with phenylsilane, 1a and 1b are far more active than 2a and 2b (entries [18][19][20][21].…”