Preparation of a novel phosphorus-phosphorus bonded diphosphine

Harris, Thomas V.; Pretzer, W. R.

doi:10.1021/ic00219a052

Cited by 15 publications

(11 citation statements)

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“…The C-P-C angle within the bicycle is constrained to be 93 • while the C-P-C angle at the PPh 2 is 101 • and is more typical of a tertiary phosphine. 11); C5-P1-P2-C15, -161.14 (10).…”

Section: Diphosphanesmentioning

confidence: 99%

“…Diphosphane 2 has been previously reported as the product obtained adventitiously from the reaction of PhobPH and 1-iodoheptafluoropropane. 10 The two chiral PCg moieties present in 1 means that it exists as rac and meso diastereoisomers. Treatment of CgP(BH 3 )Li with CgPBr gave two products assigned to rac and meso isomers of CgP(BH 3 )-PCg (1.BH 3 ) on the basis of their characteristic 31 P NMR parameters {major product: d 13.8 (br d), -4.7 (d, J PP = 363 Hz); minor product : d 14.3 (br d), -8.0 (d, J PP = 354 Hz)}.…”

Section: Diphosphanesmentioning

confidence: 99%

“…All data collections were performed using a single crystal coated in inert oil and mounted on a glass fibre. Intensities were integrated 22 from several series of exposures in j and w calculated by the Apex II 23 program after unit cell determination for structures 1, 2, 3, and 5a, for structures 1b, 4a and 7c•C 6 H 5 CH 3 intensities were integrated 24 from several series of exposures measuring 0.3 • in w. Absorption corrections were based on equivalent reflections using SADABS, 25 and structures (10) were refined against all F o 2 data with hydrogen atoms riding in calculated positions using SHELXTL. 26 A freely refining variable was used to model the occupancy of O4 in 1a.…”

Section: Crystal Structure Determinationsmentioning

confidence: 99%

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Diphosphanes derived from phobane and phosphatrioxa-adamantane: similarities, differences and anomalies

et al. 2011

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The homodiphosphanes CgP-PCg (1) and PhobP-PPhob (2) and the heterodiphosphanes CgP-PPhob (3), CgP-PPh(2) (4a), CgP-P(o-Tol)(2) (4b), CgP-PCy(2) (4c), CgP-P(t)Bu(2) (4d), PhobP-PPh(2) (5a), PhobP-P(o-Tol)(2) (5b), PhobP-PCy(2) (5c), PhobP-P(t)Bu(2) (5d) where CgP = 6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamant-9-yl and PhobP = 9-phosphabicyclo[3.3.1]nonan-9-yl have been prepared from CgP(BH(3))Li or PhobP(BH(3))Li and the appropriate halophosphine. The formation of 1 is remarkably diastereoselective, with the major isomer (97% of the product) assigned to rac-1. Restricted rotation about the P-P bond of the bulky meso-1 is detected by variable temperature (31)P NMR spectroscopy. Diphosphane 3 reacts with BH(3) to give a mixture of CgP(BH(3))-PPhob and CgP-PPhob(BH(3)) which was unexpected in view of the predicted much greater electron-richness of the PhobP site. Each of the diphosphanes was treated with dimethylacetylene dicarboxylate (DMAD) in order to determine their propensity for diphosphination. The homodiphosphanes 1 and 2 did not react with DMAD. The CgP-containing heterodiphosphanes 4a-d all added to DMAD to generate the corresponding cis alkenes CgPCH(CO(2)Me)=CH(CO(2)Me)PR(2) (6a-d) which have been used in situ to form chelate complexes of the type [MCl(2)(diphos)] (7a-d) where M = Pd or Pt. The PhobP-containing heterodiphosphanes 3 and 5a-d react anomalously with DMAD and do not give the products of diphosphination. The X-ray crystal structures of the diphosphanes 2, 3, 4a, and 5a, the monoxide and dioxide of diphosphane 1, and the platinum chelate complex 7c have been determined and their structures are discussed.

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“…The C-P-C angle within the bicycle is constrained to be 93 • while the C-P-C angle at the PPh 2 is 101 • and is more typical of a tertiary phosphine. 11); C5-P1-P2-C15, -161.14 (10).…”

Section: Diphosphanesmentioning

confidence: 99%

Section: Diphosphanesmentioning

confidence: 99%

Section: Crystal Structure Determinationsmentioning

confidence: 99%

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Diphosphanes derived from phobane and phosphatrioxa-adamantane: similarities, differences and anomalies

et al. 2011

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“…However, upon gem -dimethylation of the central carbon, P–P-bonded species were obtained as major byproducts . Earlier work by Harris and Pretzer on the synthesis of P–P diphosphines from alkyl halides reported a proposed mechanism for the formation of these species . To avoid these side reactions, subsequent synthetic efforts were focused on type III cyclic sulfate precursors that did not possess the halide groups that were implicated in their formation.…”

Section: Resultsmentioning

confidence: 99%

gem-Dialkyl Effect in Diphosphine Ligands: Synthesis, Coordination Behavior, and Application in Pd-Catalyzed Hydroformylation

et al. 2019

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A series of palladium complexes with C 3 -bridged bidentate bis(diphenylphosphino)propane ligands with substituents of varying steric bulk at the central carbon have been synthesized. The size of the gem-dialkyl substituents affects the C−C−C bond angles within the ligands and consequently the P−M−P ligand bite angles. A combination of solid-state X-ray diffraction (XRD) and density functional theory (DFT) studies has shown that an increase in substituent size results in a distortion of the 6-membered metal−ligand chair conformation toward a boat conformation, to avoid bond angle strain. The influence of the gem-dialkyl effect on the catalytic performance of the complexes in palladium-catalyzed hydroformylation of 1-octene has been investigated. While hydroformylation activity to nonanal decreases with increasing size of the gem-dialkyl substituents, a change in chemoselectivity toward nonanol via reductive hydroformylation is observed.

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“…With 1,5-cyclooctadiene and PH3, the AIBN-catalysed reaction afforded, after 5 h at 80 °C, a 1:2 mixture of the 1,4 and 1,5 adducts, 82 and 83, in 50% yield (eq. 30) [36].…”

Section: Hydrophosphination Under Radical Conditionsmentioning

confidence: 99%

Hydrophosphination of Unactivated Alkenes, Dienes and Alkynes: A Versatile and Valuable Approach for the Synthesis of Phosphines

Delacroix

Gaumont

2005

COC

141

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The last years have seen many advances in the field of organometallic catalysis. Motivating much of the work has been the potential for discovering new catalytic reactions, which can be used for the synthesis of bulky chemicals and fine chemical intermediates. Since the efficiency and the selectivity of the catalyst mainly rely on the structure of the ligand, there is a great interest in the design and the synthesis of new ligands (amines, aminoalcohols, thioether, phosphines etc). From all of them, phosphine derivatives are the most widely used with transition metal catalysts. Different approaches have allowed to prepare phosphine derivatives: nucleophilic substitution of a P-chloro derivative, nucleophilic substitution using metal phosphide, C-P cross coupling etc. A greener way to phosphines is the addition of a P-H bond to a multiple bond since no atom loss is observed (atom economy concept). These reactions are mainly carried out in the presence of radical initiators or under basic conditions. Acidic and neutral media were also proposed. A few recent examples reported the use of a metal activation. This review is designed to remember some of the early aspects of hydrophosphination reactions using phosphines, protected or not, and unactivated or slightly activated alkenes, dienes and alkynes and to focus on the more promising results obtained in this field for the last 15 years. The reactions involving pentavalent phosphorus derivatives (phosphine-oxide, thiophosphines, phosphonate and phosphate derivatives etc.) are not concerned b y this chapter.

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Preparation of a novel phosphorus-phosphorus bonded diphosphine

Cited by 15 publications

References 0 publications

Diphosphanes derived from phobane and phosphatrioxa-adamantane: similarities, differences and anomalies

Diphosphanes derived from phobane and phosphatrioxa-adamantane: similarities, differences and anomalies

gem-Dialkyl Effect in Diphosphine Ligands: Synthesis, Coordination Behavior, and Application in Pd-Catalyzed Hydroformylation

Hydrophosphination of Unactivated Alkenes, Dienes and Alkynes: A Versatile and Valuable Approach for the Synthesis of Phosphines

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