Dimetalation of Trivalent Organophosphines

Intramolecular Nucleophilic Substitution of ω-Haloalkylphosphine Derivatives

“…44: yield 1.629 g (81%); mp 78.3−79.5 °C (lit. 30 (12), 200 (M) (100), 199 (20), 185 (12), 167 (26), 166 (9), 155 (83), 153 (12), 139 (28), 138 (53), 137 (27), 123 (12), 121 (14), 109 (23), 108 (11), 107 (24), 95 (13), 94 (29), 93 (19), 92 (9), 91 (55), 79 (12), 78 (11), 77 (34), 69 (10), 65 (22), 63 (38), 62 (20), 51 (12), 47 (10), 45 (13); HRMS (ESI-TOF) m/z [M + H] + calcd for C 9 H 13 OPS 201.0497, found 201.0489. Analytical data are in accordance with the literature.…”

“…Methyldi(o-anisyl)phosphine Sulfide (21). This compound was prepared according to the general procedure from o-anisylmagnesium bromide (11.5 mL, 11.5 (38), 261 (18), 259 (11), 183 (9), 171 (34), 167 (9), 155 (20), 154 (18), 153 (18), 139 (15), 138 (11), 137 (21), 136 (9), 122 (10), 121 (100), 109 (16), 107 (15), 93 (10), 92 (56), 77 (20), 65 (11), 63 (13); HRMS (ESI-TOF) m/z [M + H] + calcd for C 15 H 17 O 2 PS 293.0760, found 293.0754.…”

“…This compound was prepared according to the general procedure from methyldiphenylphosphine sulfide (12) (0.105 g, 0.47 mmol), n-BuLi (0.43 mL, 1.6 M in hexanes, 0.70 mmol), and 1-bromo-5-chloropentane (0.093 g, 0.52 mmol) as a white solid. 15c: yield 0.102 g (67%); mp 66.0−67.5 °C; R f 0.47 (hexane/EtOAc 6:1); (15), 270 (6), 269 (29), 220 (8), 219 (15), 218 (100), 217 (15), 199 (13), 186 (7), 185 (28), 184 (6), 183 (38), 152 (9), 141 (9), 140 (55), 139 (33), 133 (5), 121 (10), 109 (12), 108 (23), 107 (18), 91 (11), 78 (5), 77 (14), 65 (6), 63 (22), 55 (9), 51 (10); HRMS (ESI-TOF) m/z [M + H] + calcd for C 18 H 22 PSCl 337.0931, found 337.0941.…”

Mono‐ und Bis(difluorphosphoranyl)ethylen, n‐Hexyliden‐fluorphosphoran und ein 2,4‐Di‐n‐pentyl‐1λ5,3λ5‐diphosphet

“…Auch Di-n-butylethenylphosphan bildet rnit n-Butyllithium in erster Stufe (a-Lithio-n-hexy1)di-n-butylphosphan. Das primare Reaktionsprodukt addiert sich jedoch an ein weiteres Molekul des Ethenylphosphans[9].Die chemische Verschiebung C~(~' P ) des n-Hexyliden-bis(diethy1amino)-fluorphosphorans, ppm, die 'J(PF)-Kopplungskonstante 988,8 Hz. lm '9-NMR-Spektrum tritt ein Dublett bei 4°F) = -83,3 ppm auf.…”

Metal Complexes of Scorpionate-Like Polyimido Sulphur Phosphanyl Ligands

“…However, direct metalation of both methyl groups is difficult which is due to the fact that deprotonation at one methyl group deactivates the second methyl group and the reaction gets too slow. [142] Usually, metal-lithium exchange reactions are conducted in order to obtain…”