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

Synthesis and Crystal Structure of Heteronuclear Metal Complexes with Nitrido Bridges Re≡N‐Ni, Re≡N‐Pt, Os≡N‐Rh, and Os≡N‐Ir The heteronuclear complex [(Me 2 PhP) 3 Br 2 Re≡N‐NiBr 2 (OPMe 2 Ph)] ( 1 ) is obtained by the reaction of [ReNBr 2 (PMe 2 Ph) 3 ] with NiBr 2 in tetrahydrofuran in form of dark green, air sensitive crystals crystallizing in the monoclinic space group P2 1 /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 [NiBr 2 (OPMe 2 Ph)] is connected by an asymmetric nitrido bridge Re≡N‐Ni with the nitrido complex [ReNBr 2 (PMe 2 Ph) 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 [ReNCl 2 (PMe 2 Ph) 3 ] with PtCl 4 in THF proceeds under reduction of Pt IV to yield air stable, brown crystals of [{(Me 2 PhP) 3 Cl 2 Re≡N} 2 PtCl 2 ] ( 2 ) with the monoclinic space group P2 1 /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 [OsNCl 3 (AsPh 3 ) 2 ] reacts with [Rh(μ‐Cl)(COD)] 2 in CH 2 Cl 2 to yield [(Ph 3 As) 2 Cl 3 Os≡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 [(Ph 3 As) 2 Cl 3 Os≡N‐IrCl(COD)] ( 4 ) is obtained by the reaction of [Ir(μ‐Cl)(COD)] 2 with [OsNCl 3 (AsPh 3 ) 2 ] in CH 2 Cl 2 . 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.