Crystal structures of hydrido-, fluoro-, and chloro-tris(triethyl-phosphine)platinum(II) salts

Abstract

Crystals of [Pt(PEt₃)₃H][PF₆] are triclinic, P, with a= 15.969(3), b= 20.600(3), c= 9.081 (2)Å, α= 79.87(2), β= 88.91(2), γ= 82.49(2)°, and Z= 4. Crystals of [Pt(PEt₃)₃F][BF₄] are monoclinic, P2₁/c with a= 15.627(13), b= 10.988(8), c= 16.347(16)Å, β= 102.7(3)°, and Z= 4. Crystals of [Pt(PEt₃)₃Cl][BF₄] are monoclinic. P2₁/n, with a= 11.507(11), b= 17.452(18), c= 14.199(20)Å, β= 104.6(4)°, and Z= 4. Least-squares refinements for these three complexes converged with R= 0.049 (4 485 reflections), R 0.045 (3 008), and 0.047 (3 634) respectively. Mean bond lengths are Pt–P(trans to H) 2.335(4), Pt–P(cis to H) 2.300(3), Pt–P (trans to F) 2.239(3), Pt–P (cis to F) 2.337(4), Pt–P (trans to Cl) 2.251(3), Pt–P (cis to Cl) 2.353(3), Pt–F 2.043(7), and Pt–Cl 2.366(3)Å. The Pt–P bond lengths trans to the anionic ligand (X) in the cations follow the expected trans-influence order, whereas those cis to X follow the order Pt–P (cis to Cl) > Pt–P (cis to F) > Pt–P (cis to H) which reflects the anionic size of X.