Electric Literature of 1608-26-0. Let¡¯s face it, organic chemistry can seem difficult to learn. Especially from a beginner¡¯s point of view. Like 1608-26-0, Name is Tris(dimethylamino)phosphine
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Iron-57 NMR and structural study of [Fe(eta5-Cp)(SnPh 3)(CO)(PR3)] (PR3 = phosphine, phosphite). Separation of steric and electronic sigma and pi effects
The complexes [Fe(Cp)(SnPh3)(CO)(PR3)] (PR 3 = PMe3 (1), PnBu3 (2), PCy 3 (3), PMe2Ph (4), PMePh2 (5), P(CH 2Ph)3 (6), PPh3 (7), P(4-MeC6H 4)3 (8), P(4-MeOC6H4)3 (9), P(4-FC6H4)3 (10), P(4-CF3C 6H4)3 (11), P(NMe2)3 (12), P(OMe)3 (13), P(OPh)3 (14)), which have been characterized by X-ray crystallography (except for 1 and 4), infrared spectroscopy (carbonyl stretching frequency, nuCO), and NMR spectroscopy (13C, 31P, 57Fe, 119Sn) offer some insight into the response of the iron nucleus to changes in the electronic and steric properties of the PR3 ligand. A fairly good correlation is found between the 57Fe chemical shift and the Tolman cone angle theta for PR3 and a rather poorer correlation between delta(57Fe) and nuCO. However, for the subseries of complexes 7-11 having PR3 = P(4-XC6H4) 3 (X = H, Me, MeO, F, CF3), the correlation between delta(57Fe) and nuCO is very good. Since the steric properties of these ligands, from the point of view of the metal, are identical (theta = 145), this provides a means of separating the steric and electronic contributions of PR3 to delta(57Fe). The electronic contribution of PR3 to delta(57Fe) can be further separated into sigma and pi components by making use of the finding that the pi component of the Fe-P bond has a negligible influence on delta(57Fe), unlike its influence on nuCO. The ligands PMe3, PnBu3, PCy3, PMe 2Ph, PMePh2, and P(NMe2)3 are found to be “pure” sigma donors, P(OMe)3 and P(OPh)3 are found to be pi acceptors of differing strength, and P(4-XC 6H4)3 is found to show weak but clearly distinguishable pi acceptor properties.
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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate