31 P‐, 119 Sn‐ and 195 Pt‐NMR. Studies of Trichlorostannate Complexes of Pt(II) and Pd(II). 2 J( 119 Sn, 117 Sn)‐Values

The synthesis and solution structures of new four‐ and five‐coordinate phosphine and arsine complexes of Pt and Pd containing the trichlorostannate ligand are described. Complexes containing two and three SnCl − 3 ‐ligands have been identified from their 31 P‐, 119 Sn‐ and 195 Pt‐NMR. spectra. The complexes trans ‐[M (SnCl 3 ) 2 L 2 ] (M = Pt, L‐PEt 3 , PPr 3 , AsEt 3 ; M = Pd, L = AsEt 3 ) show unexpectedly large 2 J( 119 Sn, 117 Sn)‐values (34,674–37,164 Hz) with the trans ‐orientation of these spins playing an important role. The heteronuclear coupling constant 2 J ( 119 Sn, 31 P) in the five‐coordinate cationic complexes [Pt(SnCl 3 )(P( o ‐AsPh 2 C 6 H 4 ) 3 )] + and [Pt(SnCl 3 )(As( o ‐PPh 2 C 6 H 4 ) 3 )] + also shows a geometric dependence. New five‐coordinate anionic complexes of type [M (SnCl 3 ) 3 L 2 ] − (M = Pd, Pt; L = PEt 3 , AsEt 3 ) may be prepared via addition of three mol‐equiv. of SnCl 2 and one mol‐equiv. of (PPN)Cl to [MCl 2 L 2 ] in acetone.