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• W2018944115 abstract "Abstract The coordination chemistry of phospha-alkynes (PCR) at electron-rich and sterically hindered {M(diphosphine) 2 } [M=Mo(0), W(0), Re(I), Fe(II)] centres, in which the PCR ligand adopts the very rare and electronically unfavoured end-on (η 1 ) coordination mode, as well as at the less sterically demanding {Rh(triphos)} + site, are described and compared with those exhibited by alkynes at the same metal centres. At the former sites, the η 1 -PCR ligand behaves as a weak π-acceptor and is typically activated to α-nucleophilic addition to give phospha-alkene, phosphine and phosphinidene oxide products, although activation towards electrophilic (protic) addition has also been recognized upon hydrometalation (insertion into a metal–H bond to give a phospha-alkenyl species). At the same metal sites, the η 2 -coordination of alkynes is unfavoured (on both electronic and steric grounds) and these substrates undergo rearrangements (H-shifts) towards η 1 -bonded alkynyl and vinylidene derivatives, or towards a less sterically demanding η 2 -allene species, and these products are activated towards β-electrophilic addition (protonation) on account of their π-electron withdrawal ability which contrasts with the behaviour of the η 1 -P-ligated phospha-alkyne and derivatives. The alkyne and phospha-alkyne insertions into an Fe–H bond are also compared, as well as their cycloaddition reactions (cyclotri- and cyclodimerisations, respectively) at the {Rh(triphos)} + centre which exhibits open coordination sites for η 2 -ligation. The above reactions are discussed in terms of both stereochemical and electronic effects." @default.
• W2018944115 created "2016-06-24" @default.
• W2018944115 creator A5081571915 @default.
• W2018944115 date "2001-08-01" @default.
• W2018944115 modified "2023-09-24" @default.
• W2018944115 title "Comparative behaviours of phospha-alkynes and alkynes at electron-rich phosphinic metal centres" @default.
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• W2018944115 doi "https://doi.org/10.1016/s0022-328x(01)00997-4" @default.
• W2018944115 hasPublicationYear "2001" @default.
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