Reactions of a Phosphinoimino-thiazoline-Based Metalloligand with Organic and Inorganic Electrophiles and Metal-Induced Ligand Rearrangements

Abstract

The reaction of the neutral Pt(II) bischelated complex cis-[Pt{Ph2PN··· C ··· NCH2CH2 S}2] ([Pt(2 −H)2], 1; 2 = Ph2PNHCNCH2CH2 S, N-(diphenylphosphino)-thiazoline-2-amine) with the organic electrophile EtNCS yielded complex [Pt(2 −H)(2 −H·EtNCS)] (3) as a result of the nucleophilic attack of the coordinated 2-((diphenylphosphino)imino)thiazolidin-3-yl moiety on the heteroallene carbon atom and coordination of the sulfur atom to the metal. The reaction of 1 with [Cu(NCMe)4]PF6 also proceeded by nucleophilic attack of the P−N nitrogen atom on Cu(I) and afforded the coordination polymer [1·Cu]∞[PF6]∞ (4). The reaction of ligand 2 with NiBr2·xH2O resulted in a molecular rearrangement and afforded an unexpected pentacoordinated diamagnetic complex, [Ni(2){trans-Ph2PNC−N(PPh2)CH2CH2 S}Br]Br (6), which likely arises from a metal-templated ligand coupling in the presence of water acting as promoter. Complex 6 was evaluated as a precatalyst for ethylene oligomerization, showing good activities with EADC as cocatalyst. All new complexes were structurally characterized by X-ray diffraction.

Unexpected Metal-Induced Isomerisms and Phosphoryl Migrations in Pt(II) and Pd(II) Complexes of the Functional Phosphine 2-(Bis(diphenylphosphino)methyl)-oxazoline

“…Phosphoryl migrations were also observed in several aminophosphine systems, showing, e.g., P−N−N to NP−N rearrangements and reversible P−N−P to NP−P tautomerisms triggered by protonation/deprotonation of N , N -bisdiphenylphosphino-pyridin-2-amine . N to N phosphoryl migrations were also reported, with one example concerning the Ni(II)-induced formation of a thiazoline-diphosphine sharing analogies with 2 and 2 ′ (see Scheme ) . Herein, we examine the coordination chemistry of ligand 1 −H with Pt(II) and Pd(II) precursors and describe some unexpected ligand rearrangements based on phosphoryl group migration.…”

Nickel Catalyzed Olefin Oligomerization and Dimerization

“…Complex 17 (Figure 10) shows moderate activity for ethylene oligomerization in the presence of AlEtCl 2 and produces mainly butenes and hexenes with low selectivity toward butene-1 (Table 5). 95 3.1.2.3. (P,P)-Neutral Ligands.…”

Synthesis and reactivity of an iridium complex based on a tridentate aminophosphano ligand

“…1, bottom). 3–6 In addition, the aminophosphano functionality has been successfully used to decorate ligating functionalities, 7 in some cases as elusive as the silylene 7 a , i and germylene 7 a groups. Remarkably, the applications of these complexes are varied and span catalysis, bond activation, metaloenzyme mimics, drugs, and redox-active multimetallic systems, among others.…”