Synthese und Struktur von dreikernigen Heterometall-Komplexen mit Nitridobrücken zwischen Re und Sn

Synthesis and Structure of Threenuclear Heterometallic Complexes with Nitrido Bridges between Re and Sn The threenuclear heterometallic complex (Me₂PhP)₂ClRe(μ-Cl)N]₂SnCl₄ results from the reaction of ReNCl₂(PMe₂Ph)₃ with SnCl₄ in CH₂Cl₂. The brown, air-sensitive complex is diamagnetic. It crystallizes with two solvate molecules as (Me₂PhP)₂ClRe(μ-Cl)N]₂SnCl₄ · 2 CH₂Cl₂ in the space group P 1 with a = 1189.1(2), b = 1262.3(2), c = 1776.7(3) pm, α = 86.04(2), β = 89.27(2), γ = 72.75(1)°, Z = 2. In the threenuclear complex two fragments (Me₂PhP)₂ClReN, which are connected by two Cl bridges, coordinate with their nitrido ligands one SnCl₄ molecule. The two resulting nitrido bridges complete the coordination of the Sn atom to a distorted octahedron with a cis arrangement of the N atoms. The bent nitrido bridges (Re–N–Sn = 155) are asymmetrical with distances Re–N = 168 pm and Sn–N = 225 pm. An incomplete exclusion of water during the synthesis leads to the formation of (Me₂PhP)₃ClRe(μ-Cl)N]Sn₂(OH)Cl₇ · 2 CH₂Cl₂ in form of air-stable, red-violett crystals (P 1, a = 1074.1(2), b = 1251.1(3), c = 1685.0(1) pm, α = 99.61(2), β = 91.49(2), γ = 92.69(2)°, Z = 2). In the diamagnetic complex one molecule ReNCl₂(PMe₂Ph)₃ is coordinated by the nitrido ligand and one Cl bridge to the Sn atoms of a unit Sn₂(OH)Cl₇. In this unit the two Sn atoms are connected by one Cl and one OH bridge. The distances in the almost linear nitrido bridge (Re–N–Sn = 164.6) are Re–N = 170.5 pm and Sn–N = 219.8 pm.