Synthese, Struktur und Eigenschaften der Komplexe [(H2O)Cl4Os≡N‐IrCl(C5Me5)(AsPh3)], [(Ph3Sb)Cl4Os≡N‐IrCl(C5Me5)(SbPh3)], [(Ph3Sb)2Cl3Os≡N‐IrCl(COD)] und [{(Me2PhP)2(CO)Cl2Re≡N}2ReNCl2(PMe2Ph)

Abstract

AbstractSynthesis, Crystal Structure, and Properties of the Complexes [(H2O)Cl4Os≡N‐IrCl(C5Me5)(AsPh3)], [(Ph3Sb)Cl4Os≡N‐IrCl(C5Me5)(SbPh3)], [(Ph3Sb)2Cl3Os≡N‐IrCl(COD)] and [{(Me2PhP)2(CO)Cl2Re≡N}2ReNCl2(PMe2Ph)]The dinuclear complexes [(H2O)Cl4Os≡N‐IrCl(C5Me5)(AsPh3)]·H2O (1·H2O), [(Ph3Sb)Cl4Os≡N‐IrCl(C5Me5)(SbPh3)] (2), and [(Ph3Sb)2Cl3Os≡N‐IrCl(COD)] (3) result from the reaction of the nitrido complexes [(Ph3As)2OsNCl3] and [(Ph3Sb)2OsNCl3] with the iridium compounds [IrCl2(C5Me5)]2 and [IrCl(COD)]2 in dichloromethane. 1 crystallizes as 1·H2O in form of green platelets in the monoclinic space group Cm and a = 1105.53(6); b = 1486.76(9); c = 2024.88(10) pm, β = 97.191(4)°, Z = 4. The formation of 1 in air involves a ligand exchange, and the coordination of a water molecule in trans position to the Os‐N triple bond. The resulting complex fragments [(H2O)Cl4Os≡N] and [IrCl(C5Me5)(AsPh3)] are connected by an asymmetric nitrido bridge Os≡N‐Ir. The nitrido bridge is characterised by an Os‐N‐Ir bond angle of 173.7(7)°, and distances Os‐N = 168(1) pm and Ir‐N = 191(1) pm. 2 crystallizes in clumped together brown platelets with the space group ${\rm P}{\bar 1}$ and a = 1023.3(3), b = 1476.2(3), c = 1872.5(6) pm, α = 74.60(2), β = 73.84(2), γ = 76.19(2)°, Z = 2. In 2 the asymmetric nitrido bridge Os≡N‐Ir joins the two complex fragments [(Ph3Sb)Cl4Os≡N] and [IrCl(C5Me5)(SbPh3)], which are formed by a ligand exchange reaction. 3 forms dark green crystals with the triclinic space group ${\rm P}{\bar 1}$ and a = 1079.4(1), b = 1172.3(1), c = 1696.7(2) pm, α = 101.192(9),β = 92.70(1), γ = 92.61(1)°, Z = 2. The distances in the almost linear nitrido bridge (Os≡N‐Ir = 175.3(7)°) are Os‐N = 171(1) pm and Ir‐N = 183(1) pm. The reaction of [ReNCl2(PMe2Ph)3] with [Mo(CO)3(NCMe)3] unexpectedly affords the trinuclear complex [{(Me2PhP)2(OC)Cl2Re≡N}2ReNCl2(PMe2Ph)] (4) as the main product. It forms triclinic brown crystals with the composition 4·2THF and the space group ${\rm P}{\bar 1}$ (a = 1382.70(7), b = 1498.58(7), c = 1760.4(1) pm, α = 99.780(7), β = 99.920(7), γ = 114.064(6)°, Z = 2). In the trinuclear complex, the central fragment, [ReNCl2(PMe2Ph)] is joined in trans position to two nitrido complexes [(Me2PhP)2(CO)Cl2Re≡N], giving an almost linear Re≡N‐Re‐N≡Re arrangement. The bond angles and distances in the nitrido bridges are Re‐N‐Re = 167.8(3)°, Re‐N = 171.1(8) pm and 204.2(8) pm; and Re‐N‐Re = 168.1(4)°, Re‐N = 170.9(9) and 203.5(9) pm respectively. As expected, the Re‐N bond length to the terminal nitrido ligand on the central Re atom is much shorter at 161.2(9) pm than the triple bonds of the asymmetric bridges.