General routes to alkyl phosphatrioxaadamantane ligands

Joanne H. Downing; Joëlle Roure; Katie Heslop; Mairi F. Haddow; Jonathan Hopewell; Matteo Lusi; Hirahataya Phetmung; A. Guy Orpen; Paul G. Pringle; Robert I. Pugh; Damaris Zambrano-Williams

doi:10.1021/om800141y

General routes to alkyl phosphatrioxaadamantane ligands

Joanne H. Downing
, Joëlle Roure
, Katie Heslop
, Mairi F. Haddow
, Jonathan Hopewell
, Matteo Lusi
, Hirahataya Phetmung
, A. Guy Orpen
, Paul G. Pringle
, Robert I. Pugh
, Damaris Zambrano-Williams

University of Bristol

Research output: Contribution to journal › Article › peer-review

Abstract

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.

Original language	English
Pages (from-to)	3216-3224
Number of pages	9
Journal	Organometallics
Volume	27
Issue number	13
DOIs	https://doi.org/10.1021/om800141y
Publication status	Published - 14 Jul 2008
Externally published	Yes

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@article{b9437393775f42d6bff2e0fe5cffe6d7,

title = "General routes to alkyl phosphatrioxaadamantane ligands",

abstract = "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.",

author = "Downing, \{Joanne H.\} and Jo{\"e}lle Roure and Katie Heslop and Haddow, \{Mairi F.\} and Jonathan Hopewell and Matteo Lusi and Hirahataya Phetmung and Orpen, \{A. Guy\} and Pringle, \{Paul G.\} and Pugh, \{Robert I.\} and Damaris Zambrano-Williams",

year = "2008",

month = jul,

day = "14",

doi = "10.1021/om800141y",

language = "English",

volume = "27",

pages = "3216--3224",

journal = "Organometallics",

issn = "0276-7333",

number = "13",

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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 - https://www.scopus.com/pages/publications/47949129496

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 -

General routes to alkyl phosphatrioxaadamantane ligands

Abstract

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