Bridged Dinuclear Tripodal Tris(amido)phosphane Complexes of Titanium and Zirconium as Diligating Building Blocks for Organometallic Polymers

Abstract

Appropriate bridging ligands allow for the preparation of bimetallic titanium and zirconium precursors to transitionmetal-containing polymers using the formally trianionic P(CH 2 NAr R ) 3 ligand (where Ar R = Ph, and 3,5-Me 2 C 6 H 3 for a and b, respectively). Lithiation of the known amidophosphane ligand precursors P(CH 2 NHAr R ) 3 (1a,b) with 3 equiv. of nBuLi cleanly provided the diethyl ether adducts P(CH 2 NAr R ) 3 Li 3 (OEt 2 ) 1.5 (2a,b). The THF adduct P(CH 2 NPh) 3 -Li 3 (THF) 5 (2a-THF) was characterized by X-ray crystallography. Protonolysis reactions were used to prepare the mononuclear titanium complexes P(CH 2 NAr R ) 3 TiOC 6 H 4 tBu (4a,b) and dinuclear species [P(CH

Phosphine- and thiophosphorane-amine ligands: Lithiation and coordination to Rh(I)

“…are very similar to those observed by Johnson et al for the tris(anion) P(CH 2 NPhLi) 3 [17]. Interestingly, Poli and co-workers [18] have shown some years ago that a-aminodiphenylphosphine ligands or their anionic species set up a solution equilibrium with Ph 2 PH or Ph 2 PLi and the corresponding imine.…”

“…This may explain why lithiation in the thiophosphorane series 2a-d failed, pentavalent phosphorus is, whatever its substitution scheme, too electron deficient to give a stable amido compound. Noteworthy, the tris(amido) derivative P(CH 2 NPhLi) 3 prepared by Johnson and co-workers [17] features as 3d the suitable combination of substituents; alkyl substituents on the phosphorus and an aryl ring at the nitrogen atom.…”

Tricarbonylmanganese(I) and –rhenium(I) Complexes of Imidazol‐Based Phosphane Ligands: Influence of the Substitution Pattern on the CO Release Properties

“…[29][30][31][32] The shift of the 31 P{ 1 H} NMR signal of 6, which is a classical coordination shift, is 15 ppm to a lower field. The 1 H NMR spectrum of bis(ligand) complex 6 shows one set of signals for the two coordinated ligands, and in the IR spectrum three bands typical of a C s -symmetrical complex are found.…”

Copper(i) iodide complexes containing new aliphatic aminophosphine ligands and diimines—luminescent properties and antibacterial activity

“…8 in the literature, although a number of structures of phosphine derivatives of general structure X = P(CH 2 NH-Ar) 3 have been reported. [7][8]38 Bond lengths and angles are summarized in Table 1. Perspective views of the phosphine molecules are depicted in Fig.…”