Phosphophosphidites Derived from BINOL

Adam Gorman; Jessica Cross; Rachel Doyle; Thomas Leonard; Paul Pringle; Hazel Sparkes

doi:10.1002/ejic.201900032

Phosphophosphidites Derived from BINOL

Adam Gorman
, Jessica Cross
, Rachel Doyle
, Thomas Leonard
, Paul Pringle^*
, Hazel Sparkes

^*Corresponding author for this work

Research output: Contribution to journal › Article (Academic Journal) › peer-review

13 Citations (Scopus)

254 Downloads (Pure)

Abstract

Phosphophosphidites of the type R ₂ P–P(binol) [where binol = the dianion of (S)-1,1′-bi-2-naphthol] are the phosphorus analogues of the ubiquitous phosphoramidites, R ₂ N–P(binol) and are readily accessed by the chlorosilane elimination reaction between R ₂ P–SiMe ₃ and Cl–P(binol). The crystal structure of iPr ₂ P–P(binol) (1) has been determined and shows a P–P bond length in the normal range. The solution reactions of 1 have been investigated, principally by ³¹ P NMR spectroscopy which has revealed that: (a) in contrast to the phosphoramidites, 1 is extremely moisture sensitive; (b) the P–P bond in 1 is cleaved upon reaction with H ₂ O, MeOH or mesitol; (c) the P–O bonds in 1 are cleaved upon reaction with pyrrolidine; (d) the integrity of 1 is retained upon coordination to BH ₃ or Mo ⁰ . The crystal structure of cis-[Mo(CO) ₄ (1) ₂ ] shows that 1 is bound to the Mo at the P(binol) site and the ν _CO of 2032 cm ^-1 indicates that 1 has similar ligand properties to a phosphonite.

Original language	English
Pages (from-to)	1633-1639
Number of pages	7
Journal	European Journal of Inorganic Chemistry
Volume	2019
Issue number	11
Early online date	28 Feb 2019
DOIs	https://doi.org/10.1002/ejic.201900032
Publication status	Published - 31 Mar 2019

Research Groups and Themes

BCS and TECS CDTs
Inorganic & Materials

Keywords

Diphosphane
phosphoramidite analogue
lewis basicity
P-P bond
Mo complex

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@article{1cabf4779d91449fab84bde79fef1e54,

title = "Phosphophosphidites Derived from BINOL",

abstract = " Phosphophosphidites of the type R 2 P–P(binol) [where binol = the dianion of (S)-1,1′-bi-2-naphthol] are the phosphorus analogues of the ubiquitous phosphoramidites, R 2 N–P(binol) and are readily accessed by the chlorosilane elimination reaction between R 2 P–SiMe 3 and Cl–P(binol). The crystal structure of iPr 2 P–P(binol) (1) has been determined and shows a P–P bond length in the normal range. The solution reactions of 1 have been investigated, principally by 31 P NMR spectroscopy which has revealed that: (a) in contrast to the phosphoramidites, 1 is extremely moisture sensitive; (b) the P–P bond in 1 is cleaved upon reaction with H 2 O, MeOH or mesitol; (c) the P–O bonds in 1 are cleaved upon reaction with pyrrolidine; (d) the integrity of 1 is retained upon coordination to BH 3 or Mo 0 . The crystal structure of cis-[Mo(CO) 4 (1) 2 ] shows that 1 is bound to the Mo at the P(binol) site and the ν CO of 2032 cm -1 indicates that 1 has similar ligand properties to a phosphonite. ",

keywords = "Diphosphane, phosphoramidite analogue, lewis basicity, P-P bond, Mo complex",

author = "Adam Gorman and Jessica Cross and Rachel Doyle and Thomas Leonard and Paul Pringle and Hazel Sparkes",

year = "2019",

month = mar,

day = "31",

doi = "10.1002/ejic.201900032",

language = "English",

volume = "2019",

pages = "1633--1639",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley-VCH Verlag",

number = "11",

}

TY - JOUR

T1 - Phosphophosphidites Derived from BINOL

AU - Gorman, Adam

AU - Cross, Jessica

AU - Doyle, Rachel

AU - Leonard, Thomas

AU - Pringle, Paul

AU - Sparkes, Hazel

PY - 2019/3/31

Y1 - 2019/3/31

N2 - Phosphophosphidites of the type R 2 P–P(binol) [where binol = the dianion of (S)-1,1′-bi-2-naphthol] are the phosphorus analogues of the ubiquitous phosphoramidites, R 2 N–P(binol) and are readily accessed by the chlorosilane elimination reaction between R 2 P–SiMe 3 and Cl–P(binol). The crystal structure of iPr 2 P–P(binol) (1) has been determined and shows a P–P bond length in the normal range. The solution reactions of 1 have been investigated, principally by 31 P NMR spectroscopy which has revealed that: (a) in contrast to the phosphoramidites, 1 is extremely moisture sensitive; (b) the P–P bond in 1 is cleaved upon reaction with H 2 O, MeOH or mesitol; (c) the P–O bonds in 1 are cleaved upon reaction with pyrrolidine; (d) the integrity of 1 is retained upon coordination to BH 3 or Mo 0 . The crystal structure of cis-[Mo(CO) 4 (1) 2 ] shows that 1 is bound to the Mo at the P(binol) site and the ν CO of 2032 cm -1 indicates that 1 has similar ligand properties to a phosphonite.

AB - Phosphophosphidites of the type R 2 P–P(binol) [where binol = the dianion of (S)-1,1′-bi-2-naphthol] are the phosphorus analogues of the ubiquitous phosphoramidites, R 2 N–P(binol) and are readily accessed by the chlorosilane elimination reaction between R 2 P–SiMe 3 and Cl–P(binol). The crystal structure of iPr 2 P–P(binol) (1) has been determined and shows a P–P bond length in the normal range. The solution reactions of 1 have been investigated, principally by 31 P NMR spectroscopy which has revealed that: (a) in contrast to the phosphoramidites, 1 is extremely moisture sensitive; (b) the P–P bond in 1 is cleaved upon reaction with H 2 O, MeOH or mesitol; (c) the P–O bonds in 1 are cleaved upon reaction with pyrrolidine; (d) the integrity of 1 is retained upon coordination to BH 3 or Mo 0 . The crystal structure of cis-[Mo(CO) 4 (1) 2 ] shows that 1 is bound to the Mo at the P(binol) site and the ν CO of 2032 cm -1 indicates that 1 has similar ligand properties to a phosphonite.

KW - Diphosphane

KW - phosphoramidite analogue

KW - lewis basicity

KW - P-P bond

KW - Mo complex

UR - https://www.scopus.com/pages/publications/85062354217

U2 - 10.1002/ejic.201900032

DO - 10.1002/ejic.201900032

M3 - Article (Academic Journal)

AN - SCOPUS:85062354217

SN - 1434-1948

VL - 2019

SP - 1633

EP - 1639

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 11

ER -

Phosphophosphidites Derived from BINOL

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Keywords

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