Synthese und Kristallstruktur von heteronuklearen Metallkomplexen mit Nitridobrücken Re≡N‐Ni, Re≡N‐Pt, Os≡N‐Rh und Os≡N‐Ir

Abstract

AbstractSynthesis and Crystal Structure of Heteronuclear Metal Complexes with Nitrido Bridges Re≡N‐Ni, Re≡N‐Pt, Os≡N‐Rh, and Os≡N‐IrThe heteronuclear complex [(Me2PhP)3Br2Re≡N‐NiBr2(OPMe2Ph)] (1) is obtained by the reaction of [ReNBr2(PMe2Ph)3] with NiBr2 in tetrahydrofuran in form of dark green, air sensitive crystals crystallizing in the monoclinic space group P21/n with a = 961.44(9), b = 3692.6(4), c = 1177.8(2) pm, β = 103.42(1)°, and Z = 4. In the dinuclear complex the complex fragment [NiBr2(OPMe2Ph)] is connected by an asymmetric nitrido bridge Re≡N‐Ni with the nitrido complex [ReNBr2(PMe2Ph)3], such that the Ni atom achieves a tetrahedral coordination. The nitrido bridge is characterized by a bond angle Re‐N‐Ni of 172.7(7)° and distances Re‐N = 169(1) and Ni‐N = 195.0(9) pm.The reaction of [ReNCl2(PMe2Ph)3] with PtCl4 in THF proceeds under reduction of PtIV to yield air stable, brown crystals of [{(Me2PhP)3Cl2Re≡N}2PtCl2] (2) with the monoclinic space group P21/c and a = 1241.3(1), b = 1734.0(1), c = 1369.7(1) pm, β = 101.32(1)°, and Z = 2. The divalent Pt atom exhibits a square planar coordination with the two rhenium(V) nitrido complexes coordinated by nitrido bridges Re≡N‐Pt in trans position. The distances in the virtually linear nitrido bridge (Re‐N‐Pt = 174.0(3)°) are Re‐N = 170.6(5) pm and Pt‐N = 196.4(5) pm.The nitrido complex [OsNCl3(AsPh3)2] reacts with [Rh(μ‐Cl)(COD)]2 in CH2Cl2 to yield [(Ph3As)2Cl3Os≡N‐RhCl(COD)] (3). The heterometallic complex forms olive green, largely air stable crystals with the monoclinic space group Cc and a = 2316.8(5), b = 1169.3(1), c = 1601.4(2) pm, β = 106.12(1)°, and Z = 4. Rh(I) exhibits a square‐planar coordination with the two π bonds of the COD ligand coordinating in cis position. The osmium nitrido complex is coordinated by a linear nitrido bridge Os≡N‐Rh (Os‐N‐Rh = 176.1(7)°) with distances Os‐N = 168(1) pm and Rh‐N = 186(1) pm.The complex [(Ph3As)2Cl3Os≡N‐IrCl(COD)] (4) is obtained by the reaction of [Ir(μ‐Cl)(COD)]2 with [OsNCl3(AsPh3)2] in CH2Cl2. 4 crystallizes isotypic to 3 in form of olive brown blocks with the space group Cc and a = 2322.1(2), b = 1167.01(6), c = 1603.8(2) pm, β = 105.927(9)°, and Z = 4. The nitrido bridge Os≡N‐Ir is characterized by the bond angle Os‐N‐Ir = 176.2(8)° and distances Os‐N = 171.2(8) pm and Ir‐N = 181.5(8) pm.