The reactivity of N-heterocyclic diphospholenes towards iron triad carbonyls

Kazakov, G. G.; Druzhkov, N. O.; Rumyantcev, Roman V.; Fukin, Georgy K.; Starikov, А. G.; Пискунов, А. В.; Cherkasov, V. K.

doi:10.1039/d3nj00450c

Cited by 2 publications

(2 citation statements)

References 86 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Major access routes to neutral phosphenium complexes are the dismutation of homoleptic metal(0) carbonyls and diphosphines , and metatheses of nucleophilic carbonyl metalates with P-halogeno-phosphines. ,, In view of the delicate nature of neutral V(CO) 6 , we considered the metathesis route as more practical for the synthesis of NHP complexes of vanadium and focused our attention on the reactions of Na[V(CO) 6 ] with bromo-diazaphospholenes 1a , b (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…Considering that neutral NHP complexes of cobalt ( III R , R = t Bu, Mes, Dipp; Dipp = 2,6-di(isopropyl)phenyl) , and manganese ( IV R , R = Mes, Dipp) are known, we posited that, analogous vanadium complexes ( V R ) featuring an unprecedented group-5 metal center might also be accessible. We report here on the first syntheses of these target compounds as well as a first approach toward exploring their reactivity …”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

N-Heterocyclic Phosphenium Complexes of Vanadium

Papendick,

Birchall,

Nieger

et al. 2024

Organometallics

View full text Add to dashboard Cite

Isolable N-heterocyclic phosphenium (NHP) complexes of vanadium were prepared by cophotolysis of Na[V(CO) 6 ] and 2-bromo-1,3,2diazaphospholenes. Single-crystal XRD studies revealed that the complexes exhibit trigonal planar coordination at phosphorus and short P−V distances indicative of phosphorus−metal double bonding. An exemplary reaction with Li[BEt 3 H] proceeded via hydride transfer to the phosphorus atom to yield an anionic secondary phosphine complex, which resisted protonation by [Et 3 NH]Cl and differed in this aspect from a previously reported manganese-based analogue. DFT calculations were carried out to analyze metal−ligand interactions in the NHP vanadium complexes and to rationalize the different behavior of the vanadium-and manganese-based species in H − /H + -transfer reactions.

show abstract