Preparation of Diethylcyanamide and Cyanoguanidine Complexes of Iridium

Diethylcyanamide [IrCl(η5‐C5Me5)(N≡CNEt2){P(OR)3}]BPh4 (1) and cyanoguanidine complexes [IrCl(η5‐C5Me5){N≡CN(H)C(NH2)=NH}{P(OR)3}]BPh4 (2) were prepared by allowing chloro compounds [IrCl2(η5‐C5Me5){P(OR)3}] to react with an excess of cyanamide or cyanoguanidine, respectively. Alternatively, complexes 2 were prepared by reacting [IrCl2(η5‐C5Me5){P(OR)3}] with an excess of cyanamide N≡CNH2. Bis(diethylcyanamide) [Ir(η5‐C5Me5) (N≡CNEt2)2{P(OR)3}](BPh4)2 (3) and bis(cyanoguanidine) derivatives [Ir(η5‐C5Me5){N≡CN=C(NH2)2}2{P(OR)3}](BPh4)2 (4) were also prepared by treating dichloro precursors [IrCl2(η5‐C5Me5){P(OR)3}] first with two equivalents of AgOTf and then with an excess of diethylcyanamide or cyanoguanidine, respectively. The compounds were characterised spectroscopically (IR and NMR) and by X‐ray crystal structure determination of [Ir(η5‐C5Me5)(N≡CNEt2)2{P(OMe)3}](BPh4)2.