Functionalised Phosphorus-Based Ligands in Early Transition Metal Chemistry

Nucleophilic Phosphinidene Complexes: Access and Applicability

“…[50] Hey-Hawkins and co-workers reported that, in the absence of a stabilizing donor ligand, on dehydrohalogenation of tantalum-complexed primary phosphine [Cp*(Cl 4 )Ta(PH 2 À Is)], the 14-electron phosphinidene complex [Cp*(Cl 2 )Ta=PÀIs] (56, 31 P d = 488.0 ppm) was isolated; no mention was made of intermediate products. [51] Lammertsma and co-workers showed that dehydrohalogenation of primary phosphine complex 48 a with the strong phosphazene base tert-butylimino-tri(pyrrolidino)phosphorane (BTPP, pK b % 26) in the absence of a ligand gave 18-electron complex 57 and one-half equivalent of the dimer [{Cp*IrCl 2 } 2 ] (58, Scheme 17 a). [52] Phosphinidene 57 , as identified by its 31 P NMR spectrum (d = 366 and À126 ppm), and suggests that the first dehydrohalogenation is faster than the second one.…”

New ferrocenylmethylphosphines – Preparation, characterisation and coordination chemistry of PH(CH2Fc)2, P(CH2Fc)3 [Fc=Fe(η5-C5H5)(η5-C5H4)] and their derivatives

“…Additionally, the P-H functionalised secondary phosphine 1 should allow the synthesis of unusual transition metal phosphanido complexes [29], and the ''superbulky" phosphonium cation of compound 8 should find applications due to its four redox-active ferrocenyl centres.…”

Nucleophile Phosphinidenkomplexe: Synthese und Anwendungen

“…Im 31 P‐NMR‐Spektrum der Reaktion von 54 mit DBU in Dichlormethan trat eine charakteristische Tieffeldresonanz bei δ =672 ppm auf, die mit dem berechneten Wert (BP86/TZP) von δ =684 ppm für das Dichlormethan‐solvatisierte Phosphiniden 55 in Einklang ist (Schema ) 50. Hey‐Hawkins und Mitarbeiter konnten durch Dehydrohalogenierung des Tantal‐komplexierten primären Phosphans [Cp*(Cl 4 )Ta(PH 2 Is)] ohne stabilisierenden Donorliganden den 14‐Elektronen‐Phosphinidenkomplex [Cp*(Cl 2 )TaPIs] ( 56 , δ ( 31 P)=488.0 ppm) isolieren; Zwischenprodukte wurden nicht erwähnt 51…”