Synthese,Struktur und Eigenschaften der Komplexe [(Me2PhP)3Cl2Re≡N‐IrCl2(C5Me5)], [(Me2PhP)3Cl2Re≡N‐IrCl(COD)], [PPh4][O3Os≡N‐IrCl2(C5Me5)] und [PPh4][O3Os≡N‐IrCl(COD)] mit Nitridobrücken Re≡N‐Ir und Os≡N‐Ir

Synthesis and Crystal Structures of the Complexes (Me₂PhP)₃Cl₂Re≡N‐IrCl₂(C₅Me₅)], (Me₂PhP)₃Cl₂Re≡N‐IrCl(COD)], PPh₄]O₃Os≡N‐IrCl₂(C₅Me₅)], and PPh₄]O₃Os≡N‐IrCl(COD)] with Nitrido bridges Re≡N‐Ir and Os≡N‐Ir The heteronuclear complexes (Me₂PhP)₃Cl₂Re≡N‐IrCl₂(C₅Me₅)] ( 1 ), (Me₂PhP)₃Cl₂Re≡N‐IrCl(COD)] ( 2 ), PPh₄]O₃Os≡N‐IrCl₂(C₅Me₅)] ( 3 ) and PPh₄]O₃Os≡N‐IrCl(COD)] ( 4 ) were obtained by the reaction of the nitrido complexes ReNCl₂(PMe₂Ph)₃] and OsO₃N]^— with the iridium compounds IrCl₂(C₅Me₅)]₂ and IrCl(COD)]₂ in benzonitrile. 1 forms red crystals with the composition 1 ·C₆H₅CN in the monoclinic space group P2₁/c and a = 1264.7(2); b = 1945.3(2); c = 1835.4(1) pm, β = 90.35(1)°, Z = 4. The complex fragment IrCl₂(C₅Me₅)] in the dinuclear complex is connected by an asymmetric nitrido bridge Re≡N‐Ir to the nitrido complex ReNCl₂(PMe₂Ph)₃]. The nitrido bridge is characterized by a Re‐N‐Ir bond angle of 179.4(2)° and distances Re‐N = 170.9(4) pm and Ir‐N = 203.3(4) pm. 2 forms brownish red, triclinic crystals with the space group P1¯ and a = 1076.6(2), b = 1373.2(2), c = 1452.4(1) pm, α = 107.513(8), β = 101.843(9), γ = 110.04(1)°, Z = 2. The nitrido bridge to the complex fragment IrCl(COD)] has a Re‐N‐Ir bond angle of 173, 8(4)° and distances Re‐N = 170, 4(8) pm and Ir‐N = 196, 2(8) pm. 3 crystallizes as monoclinic red crystals in the space group P2₁/n and a = 1449.9(2), b = 906.74(4), c = 2628.9(5) pm, β = 103.50(1)°, Z = 4. The nitrido bridge Os≡N‐Ir is slightly bent (Os‐N‐Ir = 165.0(3)°). The distances are Os‐N = 168.3(5) pm and Ir‐N = 201.9(5) pm. 4 forms dark brown, orthorhombic crystals with the space group P2₁2₁2₁ and a = 704.35(2), b = 1228.17(6), c = 3442.0(4) pm, Z = 4. The distances in the slightly bent nitrido bridge (Os‐N‐Ir = 161.8(4)°) are Os‐N = 169.3(7) pm und Ir‐N = 197.8(7) pm.