Zur Reaktion von [Cp₂TiCl]₂ und TiCl₄ mit LiE(SiMe₃)₂ (E = P, As) und P(SiMe₃)₃ Die Kristallstrukturen von [Cp₂TiP(SiMe₃)₂], [(Cp₂Ti)₂ClAs(SiMe₃)₂] und [TiCl₃ {P(SiMe₃)₃}₂]

Abstract

[Cp2TiCl]2 reagiert mit LiP(SiMe3)2 zu dem einkernigen Komplex [Cp2TiP(SiMe3)2] (3). Die Struktur des paramagnetischen 3 konnte mit Hilfe einer Kristallstrukturanalyse aufgeklärt werden. Danach wird das Titanatom von 2 Cp‐Liganden und einer P(SiMe3)2‐Gruppe koordiniert. Die an P gebundenen Atome liegen dabei in einer Ebene mit dem P‐Atom. Als ein Ergebnis der π‐Wechselwirkung zwischen Ti und P beobachtet man eine kurze TiP‐Bindungslänge von 246,7 pm. Dagegen reagiert [Cp2TiCl]2 mit LiAs(SiMe3)2 zu dem zweikernigen Komplex [(Cp2Ti)2ClAs(SiMe3)2] (4). Setzt man TiCl4 mit P(SiMe3)3 um, erhält man weiße Kristalle der Zusammensetzung [TiCl3 {P(SiMe3)3}2] (2). In 2 ist Ti trigonal bipyramidal an die Cl1−‐ und P(SiMe3)3‐Liganden gebunden.

Reactions of Lithiated Diphosphanes R2P–P(SiMe3)Li (R = tBu and iPr) with [MeNacnacTiCl2·THF] and [MeNacnacTiCl3]. Formation and Structure of TitaniumIII and TitaniumIV β-Diketiminato Complexes Bearing the Side-on Phosphanylphosphido and Phosphanylphosphinidene Functionalities

“…Thus, the t Bu 2 PP­(SiMe 3 ) moiety is terminally bonded to the metal center. The relatively short distance Ti1–P1 2.4840(15) Å is rather typical for Ti III phosphido complexes, see, for example, [Cp 2 TiP­(SiMe 3 ) 2 ] 2.467(1) Å, but it is slightly shorter than that found in [{(C 5 Me 4 )-SiMe 2 -PCy}­Ti­(NMe 2 )] 2.505(3) Å . The geometry around P1 (∑P1 = 344.14°) indicates significant extent of planarity, while the geometry around P2 (∑P2 = 319.01°) is clearly pyramidal.…”

Enhanced thermal stability of Cu–silylphosphido complexes via NHC ligation

“…Crystallographically characterized examples of M-P(SiMe 3 ) 2 have been described for other d-block metals, where the additional electron pair on phosphorus can also contribute to metal-P bonding. 24,30 Similar to the formation of the silyl-chalcogenolato complexes (R 3 P) 3 Cu-ESiMe 3 31,32 as intermediates in the formation of copper-chalcogenides, complex 3 is representative of the first step en route to the formation of polynuclear copperphosphide clusters using P(SiMe 3 ) 3 . 28,33 The isolation of similar, terminally bonded phosphido complexes when CuOAc was ligated with PR 3 has, to date, not proven to be possible in our hands, demonstrating a significant benefit of using a NHC in this area.…”

Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β‐Diketiminato Ligand

“…Moreover, these compounds are also catalytically active in the dehydrocoupling of amino‐ and phosphino‐boranes, which represents a versatile process for H 2 storage applications . In this context, special attention should be given to terminal low‐coordinated phosphido complexes with pyramidal or planar geometry . In these cases, phosphorus atom is connected only to one metal center and can exhibit either pyramidal geometry with one lone pair or planar geometry with the lone pair participating in π bonding , .…”

“…In these cases, phosphorus atom is connected only to one metal center and can exhibit either pyramidal geometry with one lone pair or planar geometry with the lone pair participating in π bonding , . It should be noted that, among the high number of bridged phosphido complexes,, there are many reports of transition metal complexes featuring non‐bridging, terminal phosphido ligands,, including some supported by nacnac ligands . However, only a handful of known terminal phosphido complexes, incorporate iron and, in most cases, these complexes are supported by carbonyl or cyclopentadienyl co‐ligands.…”