Accessing the Coordination Chemistry of Phosphorus(I) Zwitterions

Dube, Jonathan W.; Macdonald, Charles L. B.; Ragogna, Paul J.

doi:10.1002/anie.201205744

Cited by 44 publications

(58 citation statements)

References 69 publications

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“…The solid‐state structure of 8 showed that one phosphorus atom coordinated to two gold centers leaving the other phosphorus atom uncoordinated (Figure c). This coordination behavior is typical for phosphorus‐centered zwitterions, as reported by Ragogna et al . and Bertrand et al .…”

Section: Resultssupporting

confidence: 81%

Biradicaloid and Zwitterion Reactivity of Dicarbondiphosphide Stabilized with N‐Heterocyclic Carbenes

Hou

et al. 2018

Chemistry A European J

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Organic biradicals are usually very short lived species under standard laboratory conditions, which makes their experimental studies difficult. In contrast, heteroatom-substituted analogues of these biradicals show enhanced stability due to π-electron delocalization, which is why main group biradicals (or biradicaloids) of archetypical heterocyclobutanediyls have been thoroughly investigated. Herein, N-heterocyclic carbene (NHC)-stabilized dicarbondiphosphide compounds of the type (L )C P (L=NHC) were utilized to activate both single and multiple bonds in small molecules with a feasible concerted mechanism. This reactivity is explicable by considerable biradicaloid character of the dicarbondiphosphide compounds, which is further corroborated by theoretical studies. Furthermore, the dicarbondiphosphide compounds also exhibited Lewis base properties towards Lewis acids, such as borane and metal halides.

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Section: Resultssupporting

confidence: 81%

Biradicaloid and Zwitterion Reactivity of Dicarbondiphosphide Stabilized with N‐Heterocyclic Carbenes

Hou

et al. 2018

Chemistry A European J

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“…In contrast to the coordination chemistry of phosphides [22] and recent reports on complexes of related neutral ligands featuring [X-P(I)-X] (X = C, P) [23] fragments, the coordination chemistry of cations similar to 13 + has not yet been 5 tht), a very broad singlet is observed (d(P) = À67.2 ppm, Dn 1/2 = 210 Hz, compare with 13[OTf]: d(P) = À66.1 ppm, Dn 1/2 = 6 Hz). The broadening is attributed to the fast quadrupole relaxation of the 63 Cu nucleus (I = 3/2).…”

mentioning

confidence: 94%

NHC‐Mediated Synthesis of an Asymmetric, Cationic Phosphoranide, a Phosphanide, and Coinage‐Metal Phosphanido Complexes

et al. 2013

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A cationic phosphoranide featuring a normal and an abnormal imidazoliumyl substituent was prepared through the reaction of a P‐centered cation with an N‐heterocyclic carbene (NHC). The remarkable reactivity of this compound allows the formation of two‐ or three‐coordinate P‐centered cations, illustrating the ability of imidazoliumyl substituents to stabilize high‐ and low‐coordinated P atoms.

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“…The lack of progress in this area is likely attributable to the weak ligating ability of these and other cationic phosphanido species. As an example, analogous triphosphenium cations require the inclusion of an anionic group to their framework in order for them to form isolable metal complexes . In this case, the increased ligating ability may be rationalised by destabilisation of the frontier orbitals due to reduced negative hyperconjugation (π‐backbonding) from the P I centre into the flanking phosphines and the removal of the overall positive charge.…”

Section: Introductionmentioning

confidence: 99%

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

Binder

Kosnik

Macdonald

2018

Chemistry A European J

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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.

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Accessing the Coordination Chemistry of Phosphorus(I) Zwitterions

Cited by 44 publications

References 69 publications

Biradicaloid and Zwitterion Reactivity of Dicarbondiphosphide Stabilized with N‐Heterocyclic Carbenes

Biradicaloid and Zwitterion Reactivity of Dicarbondiphosphide Stabilized with N‐Heterocyclic Carbenes

NHC‐Mediated Synthesis of an Asymmetric, Cationic Phosphoranide, a Phosphanide, and Coinage‐Metal Phosphanido Complexes

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

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