Structural systematics. Part 3. Geometry deformations in triphenylphosphine fragments: a test of bonding theories in phosphine complexes

Dunne, Barry J.; Morris, Richard B.; Orpen, A. Guy

doi:10.1039/dt9910000653

Cited by 157 publications

(157 citation statements)

References 19 publications

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“…In 1991 Orpen tabulated S 4 ′ values for common phosphines using X-ray crystallographic data. 9 Given the rapid growth of the Cambridge Structural Database (CSD) to the point where it now contains over 250 000 experimental structures, roughly half of which are transition metal complexes, it was decided to reevaluate S 4 ′. One important difference is that in the present work we limited our search to transition metal complexes.…”

Section: Assessment Of the Steric Profile Of Phosphinesmentioning

confidence: 99%

“…9 Hence, not only can S 4 ′ be useful for quantifying the steric bulk of a phosphine ligand, but assessment of S 4 ′ for a particular phosphine with different metal complexes could possibly yield insight into the steric profile of the latter. In 1991 Orpen tabulated S 4 ′ values for common phosphines using X-ray crystallographic data.…”

Section: Assessment Of the Steric Profile Of Phosphinesmentioning

confidence: 99%

“…25 Boeyens et al have recently reported the use of X-ray crystallographic information for assessing the steric size of phosphites. 26 Orpen et al 9 have utilized the angles at the coordinated phosphine P for the same purposes, defining the symmetric deformation coordinate (S 4 ′) thus, The deformation coordinate is employed as the steric measure for the present research. The ease of determining S 4 ′ from both X-ray crystallography databases and computational chemistrybased geometry optimizations is a major factor in favor of the use of the symmetric deformation coordinate as a measure of steric bulk.…”

Section: Assessment Of the Steric Profile Of Phosphinesmentioning

confidence: 99%

“…Much of the analysis is couched in terms of PR 3 and CO as σ donors and as π acids, although considerable discussion remains as to the nature of the orbitals responsible for phosphine back-bonding interactions. 9 Giering and co-workers have extensively discussed the QALE (quantitative analysis of ligand effects) scheme for probing the electronic profile of phosphine and other ligands. 10 Lever et al used redox couples to quantify ligand electronic parameters.…”

Section: Introductionmentioning

confidence: 99%

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A Priori Assessment of the Stereoelectronic Profile of Phosphines and Phosphites

et al. 2003

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This research has demonstrated the utility of a rigorously calibrated, molecular mechanics/ semiempirical quantum mechanical protocol for developing stereoelectronic (Tolman) maps for phosphine ligands. A computational analysis of alkyl and aryl phosphines in common usage suggests that these ligands are quite similar stereoelectronically. A noticeable gap in the Tolman map for common phosphines is observed for large, electron-poor phosphines. Several candidates meeting these criteria were identified, the most promising of which is P(t-C 4F9)3. Phosphines in which the phosphorus participates in a ring, which comprise a very small subset of reported phosphines, have very interesting stereoelectronic properties, particularly those in which the ligating phosphorus is part of a three-membered ring. In terms of steric properties, the symmetric deformation coordinate proposed by Orpen and co-workers on the basis of crystallographic studies is calculated with sufficient accuracy using PM3(tm) to allow good confidence in predictions of novel phosphines. For quantification of the electronic properties of phosphines, we analyzed changes in the CO stretching frequency upon changing the ancillary phosphine ligands.

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Section: Assessment Of the Steric Profile Of Phosphinesmentioning

confidence: 99%

Section: Assessment Of the Steric Profile Of Phosphinesmentioning

confidence: 99%

Section: Assessment Of the Steric Profile Of Phosphinesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A Priori Assessment of the Stereoelectronic Profile of Phosphines and Phosphites

et al. 2003

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“…We and others have taken this approach. For example, we have sought to test the hypothesis that metalÐphosphine bonding has ' and p components, the latter based in part at least on the involvement of PÐC (or PÐO in phosphites) '* orbitals (Orpen & Connelly, 1990;Dunne et al, 1991;Garner & Orpen, 1993;Crispini et al, 1996). However, more fundamental questions arise from the attempt to tabulate`standard' or`typical' bond lengths.…”

Section: Discussionmentioning

confidence: 99%

Metal Complex Geometries in Small-Molecule Crystals

Orpen

1998

Acta Crystallogr D Biol Cryst

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The origins, scope and utility of compilations of metal± ligand and intraligand bond lengths based on the Cambridge Structural Database are discussed. The limitations on the apparent uncertainty of metal±ligand bond lengths derived from crystallographic data and recent evidence of metal-assisted hydrogen bonding involving ligands are reviewed in the light of the transferability of bond-length values from one crystal structure determination.

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Syntheses, Structures, and Reactions ofC-Methoxycarbonyl-Functionalized Small- and Medium-Sized P-Heterocycle Complexes

Streubel¹,

Wilkens

Rohde

et al. 1999

Eur. J. Inorg. Chem.

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Thermal ring‐opening of [{2‐bis(trimethylsilyl)methyl‐3‐ phenyl‐2H‐azaphosphirene‐ĸP}pentacarbonyltungsten(0)] (8a) in the presence of dimethyl acetylenedicarboxylate (DMAD) led to the 2,3‐bifunctionalized 1H‐phosphirene complex 9a and the 4‐phenyl‐substituted 2H‐1,2‐azaphosphole complex 10a, the latter as a by‐product. If a small amount of benzonitrile was added, complex 10a was obtained as the main product, along with a small amount of the decomplexed 2H‐1,2‐azaphosphole 11, which could not be isolated. Reaction of complex 10a with elemental sulfur furnished the corresponding PV sulfide 13. When the ring‐opening of complex 8a was performed in the presence of two equivalents of DMAD and two equivalents of dimethyl cyanamide, we obtained the 4‐dimethylamino‐substituted 2H‐1,2‐azaphosphole complex 10b, together with the diastereomeric Δ3‐1,3,2‐oxazaphospholene complexes 14a,b. On reaction of [{2‐pentamethylcyclopentadienyl‐3‐phenyl‐2H‐azaphosphirene‐ĸP}pentacarbonyltungsten(0)] (8b) and DMAD in toluene, the corresponding 1H‐phosphirene complex 9b was only formed as a transient species and the P‐coordinated P,C‐cage compound 15 was the final product. Using benzonitrile as solvent, the 4‐phenyl‐substituted 2H‐1,2‐azaphosphole complex 10c was obtained, together with the 7‐aza‐1‐phosphanorbornadiene complex 16, the latter through partial decomposition of 10c coupled with rearrangement and a Diels–Alder reaction; the ratio 10c/16 was found to depend strongly on the molar ratio of complex 8b to DMAD. A cycloaddition reaction of the 2,3‐bifunctionalized 1H‐phosphirene complex 9a with 2,3‐dimethylbutadiene furnished the bicyclic phosphirane complex 19, along with a small amount of the noncoordinated bicyclic phosphirane 20. Reaction of complex 9a with diethylamine yielded the phosphirane complex 21 as a 1,2‐addition product, the diorganophosphane complex 22 through ring‐opening of 9a, and the 3,4‐functionalized 1,2‐dihydro‐1‐phosphet‐2‐one complex 23 through an unprecedented ring‐expansion reaction; the products 21, 22, 23 were formed in a ratio of ca. 1:1:1. The structures of the 1H‐phosphirene complex 9a, the 4‐dimethylamino‐substituted 2H‐1,2‐azaphosphole complex 10b, the bicyclic phosphirane complex 19, the phosphirane complex 21, and the 1,2‐dihydro‐1‐phosphet‐2‐one complex 23 have been determined by single‐crystal X‐ray diffraction analysis.

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Structural systematics. Part 3. Geometry deformations in triphenylphosphine fragments: a test of bonding theories in phosphine complexes

Cited by 157 publications

References 19 publications

A Priori Assessment of the Stereoelectronic Profile of Phosphines and Phosphites

A Priori Assessment of the Stereoelectronic Profile of Phosphines and Phosphites

Metal Complex Geometries in Small-Molecule Crystals

Syntheses, Structures, and Reactions ofC-Methoxycarbonyl-Functionalized Small- and Medium-Sized P-Heterocycle Complexes

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