| Abstract: | Platinum(0) Complexes with Amino‐Substituted Alkynes: Novel Organometallic Building Blocks for Supramolecular Architectures and “Crystal Engineering” Homoleptic Bis(alkyne)platinum(0) compounds containing either NH2‐ or NH2‐/OH‐substituents are formed by reaction of Pt(cod)2 with alkynes as stable compounds. They can be used as variable building blocks for supramolecular networks. The crystal structure analyses of Bis(2‐amino‐2,5dimethyl‐5‐hydroxy‐hex‐3‐yne)platinum(0) ( 1 ) and of Bis(1(3‐amino‐3‐methyl‐but‐1‐inyl)‐cyclohexane‐1‐ol)platinum(0) ( 2 ) exhibit that the low‐valent Pt atom is tetrahedrally surrounded by the four sp‐hybridizated carbonatoms of the alkynes. Despite the fact that the bond lengths and ‐angles of the PtC4 units are equal, the supramolecular structures are different. While in 1 polymer strands are formed in which the bis(alkyne)‐Pt0 units are connected by (OH)2(NH2)2‐ tetrahedrons, 2 yields only a dimer containing a network of four OH‐ and two NH2‐groups. Platinum(0) complexes with cationic alkynes bearing ammonium substituents can be isolated as thermal stable compounds. The X‐ray structures of Cl( FH +)Pt(cod)]4 ( 8 ) reveals that four molecular units form a cube with both four NH3+ groups and Cl– at the corners connected by hydrogen bridges. In the bis(alkyne)Pt0 complex Cl1.5( FH +)1.5( F )0.5Pt] ( 9 ) only 1,33 of two NH2 groups are protonated and a hydrogen bridged network connects four bis(alkyne)Pt0 units (cod: cycloocta‐1.5‐diene, F : 1‐(trimethylsilylethinyl)‐1‐amino‐cyclohexane). |
