From a P-Bridging Phosphaketene to μ-Phosphinidenide and μ-Diphosphaurea Units at a Dinickel Core
Salt metathesis of dinickel(II) complex LNi Br (1; L is a dinucleating pyrazolate ligand with two β-diketiminato chelate arms) with Na(OCP) ⋅ (dioxane) yielded LNi (PCO) (2) with a P-bridging phosphaethynolate. Further reaction of 2 with benzyl isocyanide or with an N-heterocyclic carbene (NHC) trig...
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Veröffentlicht in: | Chemistry : a European journal 2024-11, p.e202404095 |
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Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | Salt metathesis of dinickel(II) complex LNi
Br (1; L is a dinucleating pyrazolate ligand with two β-diketiminato chelate arms) with Na(OCP) ⋅ (dioxane)
yielded LNi
(PCO) (2) with a P-bridging phosphaethynolate. Further reaction of 2 with benzyl isocyanide or with an N-heterocyclic carbene (NHC) triggered decarbonylation and gave LNi
(PCN-CH
Ph) (3) and LNi
P(NHC) (4) with P-bridging cyanophosphide and NHC-phosphinidenide, respectively. Electronic structure analysis indicated a μ
-η
: η
binding mode of the PCO
anion between the two Ni
ions in 2, which is even more pronounced for the [PCN(-CH
Ph)]
anion in 3. DFT assessment of the formation mechanism of 4 showed that attack at the phosphaketene-C atom is kinetically preferred but reversible and unproductive, while kinetically more demanding back-side S
2 attack at the phosphaketene-P atom triggers CO release with 4 as thermodynamic product. Nucleophilic addition at the phosphaketene-C could be demonstrated by the strongly exergonic reaction of 2 with KPPh
, giving unstable K[LNi
(P(O)CPPh
)] (5) with a P-bridging and K
-stabilized diphosphaurea derivative. All new complexes 2-5 have been comprehensively characterized, including by X-ray diffraction. |
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ISSN: | 0947-6539 1521-3765 1521-3765 |
DOI: | 10.1002/chem.202404095 |