TY - JOUR
T1 - General routes to alkyl phosphatrioxaadamantane ligands
AU - Downing, Joanne H.
AU - Roure, Joëlle
AU - Heslop, Katie
AU - Haddow, Mairi F.
AU - Hopewell, Jonathan
AU - Lusi, Matteo
AU - Phetmung, Hirahataya
AU - Orpen, A. Guy
AU - Pringle, Paul G.
AU - Pugh, Robert I.
AU - Zambrano-Williams, Damaris
PY - 2008/7/14
Y1 - 2008/7/14
N2 - The secondary phosphine CgPH (CgP = 6-phospha-2,4,8-trioxa-1,3,5,7- tetramethyladamantyl group) is made in 50% yield by a modification of the literature method (avoiding high pressures of PH3) by bubbling PH3 through an acidified solution of 2,4-pentanedione at 0 °C. Under similar conditions the ethyl analogue EtCgPH is formed from 3,5-heptanedione in 75% yield. The halophosphines CgPCl and CgPBr are made by treatment of CgPH witb N-halosuccinimide. CgPBr is also made by treatment of CgPH with Br2. Three methods are described for the synthesis of CgPR, where R = alkyl: (a) the previously reported acid-catalyzed condensation reaction of RPH2 with 2,4-pentanedione, which has been extended to R = iPr; (b) treatment of CgP(BH3)Li with RX followed by borane deprotection with Et2NH, which has been used for R = iPr, benzyl, n-C20H41; (c) treatment of CgPBr with RMgX, which has been used for R = iPr, Me. The complexes [PtCl2(CgPH)2] (1), [PdCl2(CgPH)2] (2), [PdCl2(CgPR)2] (where R = iPr (3a), Cy (3b)), and [PtCl2(CgPR)2] (where R = iPr (4a), Cy (4b), n-C20H4, (4c)) are described. The crystal structures of CgPH, CgPCl, [CgP(CH2Ph)2]Br, CgP(n-C 20H4,), and complexes 1, 3b, and 4c are reported. From the v(CO) values for trans-[RhCl(CO)(CgPX)2], the σ-donor/π- acceptor properties of CgPX are in the order X = iPr > Me > Ph > H > Cl.
AB - The secondary phosphine CgPH (CgP = 6-phospha-2,4,8-trioxa-1,3,5,7- tetramethyladamantyl group) is made in 50% yield by a modification of the literature method (avoiding high pressures of PH3) by bubbling PH3 through an acidified solution of 2,4-pentanedione at 0 °C. Under similar conditions the ethyl analogue EtCgPH is formed from 3,5-heptanedione in 75% yield. The halophosphines CgPCl and CgPBr are made by treatment of CgPH witb N-halosuccinimide. CgPBr is also made by treatment of CgPH with Br2. Three methods are described for the synthesis of CgPR, where R = alkyl: (a) the previously reported acid-catalyzed condensation reaction of RPH2 with 2,4-pentanedione, which has been extended to R = iPr; (b) treatment of CgP(BH3)Li with RX followed by borane deprotection with Et2NH, which has been used for R = iPr, benzyl, n-C20H41; (c) treatment of CgPBr with RMgX, which has been used for R = iPr, Me. The complexes [PtCl2(CgPH)2] (1), [PdCl2(CgPH)2] (2), [PdCl2(CgPR)2] (where R = iPr (3a), Cy (3b)), and [PtCl2(CgPR)2] (where R = iPr (4a), Cy (4b), n-C20H4, (4c)) are described. The crystal structures of CgPH, CgPCl, [CgP(CH2Ph)2]Br, CgP(n-C 20H4,), and complexes 1, 3b, and 4c are reported. From the v(CO) values for trans-[RhCl(CO)(CgPX)2], the σ-donor/π- acceptor properties of CgPX are in the order X = iPr > Me > Ph > H > Cl.
UR - http://www.scopus.com/inward/record.url?scp=47949129496&partnerID=8YFLogxK
U2 - 10.1021/om800141y
DO - 10.1021/om800141y
M3 - Article
AN - SCOPUS:47949129496
SN - 0276-7333
VL - 27
SP - 3216
EP - 3224
JO - Organometallics
JF - Organometallics
IS - 13
ER -