Trans‐Amidate Platinum Complexes Anchoring Water and N‐donor Molecules. The Importance of Hydrogen Bonding

The square planar bisnitrile platinum(II) derivatives PtCl2(NCR)2 (R=Ph (1 a); Et b); p-C6H4F c); p-C6H4tBu d); m-C6H3Me2 e); o,p-C6H2Me3 f)) react with tetrabutylammonium hydroxide to render the monoaquo [NBu4][trans-PtCl(HNCOR)2(OH2)] (2 a–2 f). water molecule is σ-coordinated platinum and binding reinforced by two strong hydrogen bonds neighboring amidate ligands (OH⋅⋅⋅OC). Substitution of in 2 a N-donor can be efficiently achieved only presence dehydrating agent as magnesium sulphate or 4 Å molecular sieves. By following this strategy, compounds [NBu4][trans-PtCl(HNCOPh)2(NH2R’)] (R’=H (3), NH2 (4), tBu (5 a), p-C6H4Me b) have been isolated. incoming are also establish amidates (NH⋅⋅⋅OC). Treatment halogens causes oxidation at metal center, rendering platinum(IV) [NBu4][PtClX2(HNCOPh)2(OH2)] (X=Cl (6 Br b), I c)).