Synthesis, reactivity, and coordination chemistry of secondary phosphines

Nell, Bryan P.; Tyler, David R.

doi:10.1016/j.ccr.2014.07.002

Cited by 33 publications

(36 citation statements)

References 147 publications

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“…We have demonstrated this for dinuclear iron and ruthenium species, e.g., and, currently, we intend to extend our investigations on dinuclear rhodium complexes. Some time ago, the coordination chemistry of secondary phosphines was reviewed and important synthetic applications of complexes bearing these ligands were reported . Recently we described the synthesis and crystal structure of the olefinic complex [RhCp(coe)(P t Bu 2 H)] (coe = cis ‐cyclooctene) which was obtained by reacting [RhCp(coe) 2 ] ( 1 ) with the corresponding secondary phosphine in refluxing toluene .…”

Section: Introductionmentioning

confidence: 99%

An Entry to Double Phosphanyl‐Bridged Dinuclear Rhodium(II) Complexes

et al. 2019

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The reaction of [RhCp(coe) 2 ] (1, coe = cis-cyclooctene) with one equivalent of the secondary phosphines PR 2 H in refluxing toluene afforded in situ the new complexes [RhCp(coe)(PR 2 H)] (R = Ph, 2a; R = o-tolyl, 2b; R = tBu, 2c) in good yields. Further thermolysis of 2a and 2b, respectively, in refluxing xylene resulted in the formation of the dinuclear doubly phosphanyl-bridged rhodium(II) species [{RhCp(μ-PR 2 )} 2 ] (3a and 3b). This thermolytic approach does not work in the case of 2c since the tBu substituents increase the electron density on the rhodium center and impede, therefore, the loss of the [a]

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Section: Introductionmentioning

confidence: 99%

An Entry to Double Phosphanyl‐Bridged Dinuclear Rhodium(II) Complexes

et al. 2019

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“…Selective formation of P-C bonds for the preparation of organophosphorus derivatives is still a topical challenging area of research despite the universality of phosphines in synthetic and catalytic methodologies, 2,[18][19][20][21] which usually exhibited an impressive functional group tolerance in comparison to classical routes. 22 Gaumont and Taillefer reported an interesting regioselective hydrophosphination of styrenes (Scheme 1): 23 Indeed, the regioselectivity of the α-or β-phosphinylation of styrenes with diphenylphosphine can be reached by selecting the iron salt (FeCl 3 or FeCl 2 , respectively, 30 mol%).…”

Section: Hydrophosphinationmentioning

confidence: 99%

Organophosphorus and Iron Catalysis: Good Partners for Hydrometalation of Olefins and Alkynes

Wei

Darcel

2020

J. Org. Chem.

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The last decades have seen an impressive development of iron complexes involving organophosphorus ligands applied in homogeneous catalyzed hydrometalation of olefins and alkynes. Two main topics will be covered in this JOCSynopsis: (i) an overview of the achievements in the area of iron-catalyzed hydrophosphination and then (ii) hydrosilylation, hydroborylation, and hydromagnesiation reactions promoted by catalysts based on organophosphorus ligands and iron.

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“…Thus, the synthesis and reactivity of Ru(η 5 indenyl) mixed phosphine complexes are important to our ongoing studies and optimization of hydrophosphination catalysis, and we have a particular interest in evaluating the behavior of secondary phosphines within the Ru coordination sphere. 7…”

Section: Introductionmentioning

confidence: 99%

Competitive Ligand Exchange and Dissociation in Ru Indenyl Complexes

Belli¹,

Wu²,

Ji³

et al. 2018

Preprint

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Kinetic profiles obtained from monitoring the solution phase substitution chemistry of [Ru(η5-indenyl)(NCPh)(PPh3)2]+ (1) by both ESI-MS and 31P{1H} NMR are essentially identical, despite an enormous difference in sample concentrations for these complementary techniques. These studies demonstrate dissociative substitution of the NCPh ligand in 1. Competition experiments using different secondary phosphine reagents provide a ranking of phosphine donor abilities at this relatively crowded half-sandwich complex: PEt2H > PPh2H >> PCy2H. The impact of steric congestion at Ru is evident also in reactions of 1 with tertiary phosphines; initial substitution products [Ru(η5-indenyl)(PR3)(PPh3)2]+ rapidly lose PPh3, enabling competitive recoordination of NCPh. Further solution experiments, relevant to the use of 1 in catalytic hydrophosphination, show that PPh2H out-competes PPh2CH2CH2CO2But (the product of hydrophosphination of tert-butyl acrylate by PPh2H) for coordination to Ru, even in the presence of a ten-fold excess of the tertiary phosphine. Additional information on relative phosphine binding strengths was obtained from gas-phase MS/MS experiments, including collision-induced dissociation (CID) experiments on the mixed phosphine complexes [Ru(η5-indenyl)PP’P’’]+, which ultimately appear in solution during the secondary phosphine competition experiments. Unexpectedly, unsaturated complexes [Ru(η5-indenyl)(PR2H)(PPh3)]+, generated in the gas-phase, undergo preferential loss of PR2H. We propose competing orthometallation of PPh3 is responsible for the surprising stability of the [Ru(η5-indenyl)(PPh3)]+ fragment under these conditions.

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Synthesis, reactivity, and coordination chemistry of secondary phosphines

Cited by 33 publications

References 147 publications

An Entry to Double Phosphanyl‐Bridged Dinuclear Rhodium(II) Complexes

An Entry to Double Phosphanyl‐Bridged Dinuclear Rhodium(II) Complexes

Organophosphorus and Iron Catalysis: Good Partners for Hydrometalation of Olefins and Alkynes

Competitive Ligand Exchange and Dissociation in Ru Indenyl Complexes

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