Remarkably stable chelating bis-N-heterocyclic carbene adducts of phosphorus( i ) cations

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The reductive dehalogenation of a zwitterionic GeII species to make a zwitterionic GeI dimer with a 1,2‐dicationic core is reported herein. To the root of the stability of this compound, the molecular and electronic structures were comprehensively characterized and investigated using crystallographic, spectroscopic, and computational methods. It was determined that the Ge centers are attracted because they are both electron‐rich and positively charged. A comparison to the electronic structure in triphosphenium cations revealed varying degrees of covalent bonding and that this difference can be distinguished spectroscopically.

Section: Resultsmentioning

confidence: 76%

A Comprehensive Investigation of a Zwitterionic Ge^I Dimer with a 1,2‐Dicationic Core

Béland

Wang

Macdonald

et al. 2019

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“…Our group has developed an efficient route to phosphamethine cyanines (which can be considered as NHC‐stabilised phosphorus(I) cations when delocalisation of the π‐type lone pair on phosphorus is minimised) involving P + transfer from a triphosphenium salt . We also showed that one of these cations, [L] + , may bind one or two equivalents of gold(I) chloride .…”

Section: Introductionmentioning

confidence: 99%

Assessing the Ligand Properties of NHC‐Stabilised Phosphorus(I) Cations

Binder

Kosnik

Macdonald

2018

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The isolation and full characterisation of a series of cationic metal-carbonyl complexes bearing an N-heterocyclic carbene stabilised phosphorus(I) ligand are reported. Specifically, the mononuclear coordination complexes [LM(CO) ][BPh ] (M=Cr, Mo, W), [LFe(CO) ][BPh ] and the dinuclear complexes [LMn (CO) ][BPh ] and [LCo (CO) ][BPh ], in which L=[bis(1,3,4,5-tetramethylimidazol-2-ylidene)phosphanide] , have all been isolated in the solid state and structurally confirmed by single-crystal X-ray diffraction. The dicationic platinum complex trans-[L PtCl ][BPh ] is also reported and fully characterised. The donor ability of [L] has been assessed by IR spectroscopy of its metal-carbonyl complexes and by using DFT calculations. The results suggest that [L] is a weak π-acceptor with moderate donor strength and thus it bridges the gap that exists between phosphines and amines in terms of ligand properties. Collectively, these molecules represent the first crystallographically characterised cationic metal-carbonyl derivatives of a P -centred ligand and are a rare collection of cationic metal-carbonyl complexes.

“…Schmidpeter had observed early on that cyanide ions displace 1,2‐bis(diphenylphosphino)ethane (dppe) from a triphosphenium cation to form DCP anions in solution using 31 P NMR spectroscopy . Indeed, nucleophilic substitution of the phosphine ligands from triphosphenium cations has been used by our group as a conceptually simple and practical method for the generation of new or useful univalent phosphorus containing molecules and oligomers . Using these results as a basis, we investigated the reactions of [dppeP][Br] and commercial cyanide sources like [K][CN], [Na][CN] and [ n Bu 4 N][CN] in the hopes of finding a safe, straightforward method of synthesizing and isolating DCP salts.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Heavy Dicyanamide Homologues from Air‐Stable Precursors

Binder

Kosnik

Onge

et al. 2018

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A convenient synthesis of dicyanophosphide and dicyanoarsenide anions is reported. These heavy homologues of the long-known and fundamentally important dicyanamide anion were formed through the nucleophilic displacement of bis(diphenylphosphino)ethane (dppe) from the pnictogen transfer agents [dppePn][BPh ] (Pn=P, As) by exposure to cyanide salts. The protocol requires three synthetic steps from commercially available materials and the [dppePn][BPh ] salts are remarkably temperature, air, and moisture stable. All products have been fully characterized by spectroscopic methods and by single-crystal X-ray diffraction, and the electronic structures of the DCPn anions have been assessed computationally.