Silylierte Phosphanimin‐Komplexe von Chrom(II), Palladium(II) und Kupfer(II). Die Kristallstrukturen von [CrCl₂(Me₃SiNPMe₃)₂], [PdCl₂(Me₃SiNPEt₃)₂] und [CuCl₂(Me₃SiNPMe₃)]₂

Abstract

Die Titelverbindungen entstehen bei der Einwirkung der silylierten Phosphanimine Me3SiNPR3 (R = CH3, C2H5) auf CrCl2(THF)2, PdCl2 und CuCl2 in Dichlormethan‐Suspension. Die drei Donor‐Acceptor‐Komplexe werden durch ihre IR‐Spektren und durch Kristallstrukturanalysen charakterisiert. [CrCl2(Me3SiNPMe3)2]: Raumgruppe Pccn, Z = 4, Strukturlösung mit 2104 unabhängigen beobachteten Reflexen, R = 0,045. Gitterkonstanten bei −70°C: a = 1326,3; b = 1562,5; c = 1171,5 pm. In der monomeren Molekülstruktur ist das Chromatom planar in der trans‐Konfiguration von den Cl‐Atomen und den N‐Atomen der Phosphanimin‐Liganden koordiniert mit Abständen CrCl = 235,94 pm und CrN = 211,7 pm. [PdCl2(Me3SiNPEt3)2]: Raumgruppe P21/n, Z = 2, Strukturlösung mit 2412 unabhängigen beobachteten Reflexen, R = 0,031. Gitterkonstanten bei 20°C: a = 917,3; b = 1390,2; c = 1161,7 pm, β = 95,80°. In der monomeren Molekülstruktur ist das Palladiumatom planar in der trans‐Konfiguration von den Cl‐Atomen und den N‐Atomen der Phosphaniminliganden koordiniert mit Abständen PdCl = 222,9 pm und PdN = 209,5 pm. [CuCl2(Me3SiNPMe3)]2: Raumgruppe Pbca, Z = 4, Strukturlösung mit 1861 unabhängigen beobachteten Reflexen, R = 0,067. Gitterkonstanten bei −70°C: a = 1440,2; b = 1205,1; c = 1536,5 pm. Die Verbindung bildet zentrosymmetrische dimere Moleküle, in denen die Cu‐Atome über nahezu symmetrische Chlorobrücken mit CuCl‐Abständen von 231,4 pm verknüpft sind. Der Abstand CuN beträgt 196,7 pm.

Synthesis, Structure, and Reactivity of an Unusual Platinum Olefin Carbene Complex, [(η4-cod)Pt{C(Ph2PNSiMe3)2-κC,κN}]

“…Both of the P−C(carbene) lengths in 2 , particularly that of the endocyclic bond, are considerably shorter than that found for P−C(methylene) in H 2 - 1 5 (1.697(5) (endo) and 1.721(5) (exo) vs 1.827(1) Å), while the P−N distances, again particularly that of the endocyclic bond, are appreciably longer (1.631(4) (endo) and 1.550(4) Å (exo) vs 1.539(2) Å). In addition, the Pt−N bond in 2 (2.092(4) Å) is shorter than those of the related Pt complexes [PtCl(PEt 3 ){CH(Ph 2 PN- p -tolyl)(Ph 2 PNH- p -tolyl)-κ C ,κ N }][PtCl 3 (PEt 3 )] (2.124(8) Å) and [PtCl(PPhMe 2 ){CH(Ph 2 PN- p -tolyl) 2 -κ C ,κ N }] (2.132(4) Å) but identical in length with that of [PdCl 2 (Me 3 SiNPEt 3 ) 2 ] (2.095 Å) . This may reflect either partial double-bond character of the Pt−N bond or simply the strong Lewis basicity of silylated phosphineimines.…”

Divergent uranium- versus phosphorus-based reduction of Me3SiN3 with steric modification of phosphido ligands

“…48 In that case, the reduced dinitrogen oxidizes the phosphorus but without ligand addition to phosphorus. In fact, silylated iminophosphanes, (R 3 SiNPR 3 ), are common starting materials to form transition metal complexes, [49][50][51][52] however, in no case has the silyl been observed to migrate to phosphorus. We note that recently a mesityl ligand has been observed to migrate from nitrogen to phosphorus.…”

Ferromagnetic Spin Ladder System: Stack of Chlorido‐Bridged Dinuclear Copper(II) Complexes with 2‐Methylisothiazol‐3(2H)‐one

“…Furthermore, the use of bulky monodentate ligands may not be favorable for the construction of spin-ladder structures. Cu(μ-Cl) 2 Cu complexes containing monodentate ligands, for example, [{Cu II Cl-(tempo)} 2 (μ-Cl) 2 ] (tempo = 2,2,6,6-tetramethylpiperidine-1-oxyl), [35] [{Cu II Cl(Me 3 SiNPMe 3 )} 2 (μ-Cl) 2 ], [36] and [{Cu II Cl(Me 3 SiNPPh 3 )} 2 (μ-Cl) 2 ], [37] have been synthesized; however, they did not form spin-ladder structures in the crystal. In summary, the use of monodentate ligands, but not bulky ones, may be suitable for the construction of the ladder structure.…”