Darstellung,Kristallstrukturen und Schwingungsspektren von trans‐[Pt(N3)4X2]2–, X = Cl,Br, I |
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Authors: | S Schrder W Preetz |
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Abstract: | Synthesis, Crystal Structures, and Vibrational Spectra of trans ‐Pt(N3)4X2]2–, X = Cl, Br, I By oxidative addition to (n‐Bu4N)2Pt(N3)4] with the elemental halogens in dichloromethane trans‐(n‐Bu4N)2Pt(N3)4X2], X = Cl, Br, I are formed. X‐ray structure determinations on single crystals of trans‐(Ph4P)2Pt(N3)4Cl2] (triclinic, space group P1, a = 10.352(1), b = 10.438(2), c = 11.890(2) Å, α = 91.808(12), β = 100.676(12), γ = 113.980(10)°, Z = 1), trans‐(Ph4P)2Pt(N3)4Br2] (triclinic, space group P1, a = 10.336(1), b = 10.536(1), c = 12.119(2) Å, α = 91.762(12), β = 101.135(12), γ = 112.867(10)°, Z = 1) and trans‐(Ph4P)2Pt(N3)4I2] (triclinic, space group P1, a = 10.186(2), b = 10.506(2), c = 12.219(2) Å, α = 91.847(16), β = 101.385(14), γ = 111.965(18)°, Z = 1) reveal, that the compounds crystallize isotypically with octahedral centrosymmetric complex anions. The bond lengths are Pt–Cl = 2.324, Pt–Br = 2.472, Pt–I = 2.619 and Pt–N = 2.052–2.122 Å. The approximate linear Azidoligands with Nα–Nβ–Nγ‐angles = 172.1–176.8° are bonded with Pt–Nα–Nβ‐angles = 116.2–121.9°. In the vibrational spectra the platinum halogen stretching vibrations of trans‐(n‐Bu4N)2Pt(N3)4X2] are observed in the range of 327–337 (X = Cl), at 202 (Br) and in the range of 145–165 cm–1 (I), respectively. The platinum azide stretching modes of the three complex salts are in the range of 401–421 cm–1. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are fd(PtCl) = 1.90, fd(PtBr) = 1.64, fd(PtI) = 1.22, fd(PtNα) = 2.20–2.27 and fd(NαNβ, NβNγ) = 12.44 mdyn/Å. |
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Keywords: | Platinum Azides Crystal structure Vibrational spectroscopy |
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