Related Experiment Video
Updated: Aug 5, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Reactivity of a dimeric yttrium bis(trimethyl)silylphosphide complex towards heteroallenes and nitriles
Hannah S Redmill1, Guillermo Garcia-Figueras Mateos1, Avantika Hasija1
1Department of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK. david.mills@manchester.ac.uk.
Abstract:
While the reactivity profiles of rare earth bis(trimethylsilyl)amides (N″ = {N(SiMe3)2}-) are well-understood, there have been few reactivity studies of rare earth bis(trimethylsilyl)phosphide (P″ = {P(SiMe3)2}-) complexes. Here we report reactions of the dimeric solvent-free yttrium phosphide complex [Y(P″)2(μ-P″)]2 (1-Y) towards a selected range of heteroallenes and nitriles. Treatment of 1-Y with N,N'-dicyclohexylcarbodiimide gives the homoleptic monomeric yttrium phosphaguanidinate complex [Y{(NCy)2CP″-κ2-N,N'}3] (2-Y), whereas reaction of 1-Y with cyclohexylisocyanate gives the heteroleptic dimeric yttrium phosphaureate siloxide complex [Y{OC(NCy)(P″)-κ2-N,O}2(µ-OSiMe3)]2 (3-Y). Conversely, 1-Y reacts with ethyl- or cyclohexyl-isothiocyanate to give the heteroleptic dimeric yttrium phosphathioureate phosphide complex [Y{SC(NEt)(P″)-κ2-N,S}2(µ-P″)]2 (4-Y) and homoleptic monomeric yttrium phosphathioureate complex [Y{SC(NCy)CP″-κ2-S,N}3] (5-Y), respectively. By contrast, 1-Y reacts with adamantyl- and tert-butyl-nitrile to give the respective yttrium phosphide solvated adducts fac-[Y(P″)3(NCAd)3] (6-Y) and [Y(P″)3(NCtBu)2] (7-Y), with no observed migratory insertion into Y-P bonds. All products were characterised by multinuclear NMR and ATR-IR spectroscopy, single crystal X-ray diffraction, and elemental analysis. Together, this work shows the strong dependence of the reactivity of rare earth phosphide complexes on substrate donor atom identity and steric profile, giving rise to both migratory insertion and ligand rearrangement pathways.
More Related Videos
10:10Application of Elemental Lanthanides in the Selective C-F Activation of Trifluoromethylated Benzofulvenes Providing Access to Various Difluoroalkenes
Published on: July 28, 2018
19:58Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Related Concept Videos
Aldehydes and Ketones to Alkenes: Wittig Reaction Overview
Electrophilic Addition to Alkynes: Halogenation
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Preparation and Reactions of Sulfides
Aldehydes and Ketones to Alkenes: Wittig Reaction Mechanism
The reaction begins with the nucleophilic addition between a phosphorus ylide and the carbonyl compound. Due to its carbanionic character, phosphorus ylide acts as a strong nucleophile and attacks the electrophilic carbonyl group. This generates a charge-separated dipolar intermediate called betaine. The negatively charged oxygen atom and...
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
Radical Reactivity: Nucleophilic Radicals