Ligand Stereoelectronic Effects in Complexes of Phospholanes, Phosphinanes, and Phosphepanes and Their Implications for Hydroformylation Catalysis

Baber, R. Angharad; Haddow, Mairi F.; Middleton, Ann J.; Orpen, A. Guy; Pringle, Paul G.; Haynes, Anthony; Williams, Gary L.; Papp, Rainer

doi:10.1021/om060912v

Cited by 55 publications

(63 citation statements)

References 39 publications

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“…The structure ( Figure 4) has the expected octahedral arrangement of ligands with phenop trans to a single carbonyl and the remaining CO donors coplanar. The W-P bond length of 2.6292(10) Å is long for this type of complex when compared to related structurally characterised derivatives such as [W(CO) 5 (PMe 3 )] [2.516(2) Å], [15] [W(CO) 5 [17] but is shorter than the value of 2.686 Å observed in the tri-tertbutylphosphane analogue. [18] As expected the W-C bond length to the carbonyl carbon trans to the phosphane is the shortest at 1.985(5) Å compared to the other W-C bond lengths which are all longer than 2.040 Å.…”

Section: Syntheses and Structure Of The Metal Complexes Of Phenopmentioning

confidence: 89%

“…Yellow [W(CO) 5 (κ 1 -phenop)] (4) was isolated in good yield from the 1:1 reaction of [W(CO) 5 (THF)] and phenop in THF. The isolated complex is freely soluble in most common organic solvents, and is air-stable in the solid state.…”

Section: Syntheses and Structure Of The Metal Complexes Of Phenopmentioning

confidence: 99%

“…Phosphacycles may not show the same level of flexibility because of their confinement within the ring which will impact on the donating ability of the ligand. [5] The so-called phobane ligands are a good example of bicyclic systems (and are one of the few such classes that have found application in industry) which show isomer-dependent basicity/reactivity allowing the separation of the symmetric and asymmetric forms by selective protonation, oxidation or deformylation. [6] Thus (diastereo)-isomers of phosphacycles can possess different characteristics that can ultimately impact on their coordination ability and/or potential in metal-based catalysis.…”

Section: Introductionmentioning

confidence: 99%

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Metal Complexes of a Structurally Embellished Phosphinane Ligand: An Assessment of Stereoelectronic Effects

et al. 2011

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The stereoelectronic features of the pentacyclic phosphane (1S,4R,4aS,5aR,6R,9S,9aS,10aR)‐4,6,11,11,12,12‐hexamethyl‐10‐phenyldodecahydro‐1,4:6,9‐dimethanophenoxaphosphinine (phenop) have been explored through a range of empirical methods including single‐crystal X‐ray structure determinations of the sulfide derivative phenopS (1), the selenide phenopSe (2), [Fe(CO)4(κ1‐phenop)] (3), [W(CO)5(κ1‐phenop)] (4) and trans‐[Rh(κ1‐phenop)(CO)Cl] (5). Cone angles derived from the structural data range from 164–203° with the smaller values being observed for the compounds possessing a phenyl group that is orthogonal to the P–Z bond and the larger values for the compounds expressing a parallel phenyl ring orientation. The cone angle data suggest a moderately bulky phosphane comparable, in steric terms, to PCy3. This is further borne out on inspection of the M–P bond lengths which tend towards the longer end of the known scale. Some flexibility is observed in the central ring which approximates to a boat conformation at one extreme and an envelope at the other depending on the nature of the P‐substituent. The electronic properties of κ1‐phenop have been assessed using a combination of infrared and NMR spectroscopy. The absolute value of the one‐bond coupling constants 1JP‐Se and 1JP‐Rh are very close to those reported for PPh3, suggesting a close analogy between κ1‐phenop and the well known triphenylphosphane. In addition, relevant υ(CO) stretches in the IR spectra of the metal carbonyl complexes also closely mimic those for the analogous complexes containing PPh3. These conclusions are supported by molecular electrostatic potential calculations at the DFT level which place phenop close to PPh3 in terms of lone pair availability.

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Section: Syntheses and Structure Of The Metal Complexes Of Phenopmentioning

confidence: 89%

Section: Syntheses and Structure Of The Metal Complexes Of Phenopmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Metal Complexes of a Structurally Embellished Phosphinane Ligand: An Assessment of Stereoelectronic Effects

et al. 2011

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“…Prigle et al reported the synthesis of the platinum complexes of several 5-, 6-and 7-membered P-heterocycles [33,34]. Gouygou et al synthesized a few bisphosphole platinum-complexes [35].…”

Section: Introductionmentioning

confidence: 99%

A study on the optical resolution of 1-isopropyl-3-methyl-3-phospholene 1-oxide and its use in the synthesis of borane and platinum complexes

Bagi

Juhász

Timári

et al. 2015

Journal of Organometallic Chemistry

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A 1-isopropyl-3-phospholene 1-oxide was prepared and the two enantiomers were isolated from the racemate by resolution using optically active TADDOL derivatives or the acidic Ca 2+ salts of (-)-O,O-diaroyl-(2R,3R)-tartaric acids. The single crystal X-ray structure of the 2 1-isopropyl-3-phospholene oxide -spiro-TADDOL 1:2 associate revealed the mode of binding between the host and guest molecules. The role of the interactions between the three molecules was supported not only by the contact data, but also force field and semiempirical calculations. Beside X-ray analysis, the absolute configuration of the P-stereogenic center was also determined on the basis of CD spectroscopy and high level quantum chemical calculations. The racemic and optically active 1-isopropyl-3-phospholenes obtained after deoxygenation were converted to the corresponding borane complexes and Pt(II) complexes.Stereostructure of the latter species was evaluated by high level quantum chemical calculations and the Pt complexes were tested as catalysts in the hydroformylation of styrene.

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“…However, bimetallic catalysis has attracted considerable interest in recent years [19][20][21][22][23][24][25].…”

Section: Introductionmentioning

confidence: 99%

Hydroformylation of Synthetic Naphtha Catalyzed by a Dinuclear gem-Dithiolato-Bridged Rhodium(I) Complex~!2009-09-28~!2009-12-18~!2010-04-23~!

Pardey

Suárez²,

Ortega³

et al. 2010

TOCATJ

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This work focuses on the use of a gem-dithiolato-bridged rhodium(I) [Rh 2 (μ-S 2 CBn 2 )(cod) 2 ] complex (cod = 1,5-cyclooctadiene, Bn 2 CS 2 2 = 1,3-diphenyl-2,2-dithiolatopropane) dissolved in toluene in the presence of monodentate phosphite P-donor ligand (P(OPh) 3 ) under carbon monoxide/hydrogen (1:1, syngas) atmosphere as an effective catalyst for hydroformylation of some olefins (oxo-reactions). The capability of this system to catalyze the hydroformylation of hex-1-ene, cyclohexene, 2,3-dimethyl-but-1-ene and 2-methyl-pent-2-ene and their quaternary mixture (synthetic naphtha) has been demonstrated. This innovative method to perform the in situ hydroformylation of the olefins present in naphthas to oxygenated products would be a promissory work for a future industrial catalytic process applicable to gasoline improving based on oxo-reactions. An important observation is that variation of CO/H 2 pressure (6.8 34.0 atm), temperature (60 80 ºC), reaction time (2 10 h), rhodium concentration ((1.0 1.8)x10-3 mol/L) affect hydroformylation reaction rates. Optimal conversion to oxygenated products were achieved under [Rh] = 1.8 x10 -2 mol/L, P(CO/H 2 ) = 34 atm (CO/H 2 = 1:1) at 80 ºC for 10 h.

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Ligand Stereoelectronic Effects in Complexes of Phospholanes, Phosphinanes, and Phosphepanes and Their Implications for Hydroformylation Catalysis

Cited by 55 publications

References 39 publications

Metal Complexes of a Structurally Embellished Phosphinane Ligand: An Assessment of Stereoelectronic Effects

Metal Complexes of a Structurally Embellished Phosphinane Ligand: An Assessment of Stereoelectronic Effects

A study on the optical resolution of 1-isopropyl-3-methyl-3-phospholene 1-oxide and its use in the synthesis of borane and platinum complexes

Hydroformylation of Synthetic Naphtha Catalyzed by a Dinuclear gem-Dithiolato-Bridged Rhodium(I) Complex~!2009-09-28~!2009-12-18~!2010-04-23~!

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