Structure-basicity relations among phosphate and phosphite esters. CNDO/2 and protonation studies

Griend, vande Lj; Verkade, J. G.; Pennings, J. F. M.; Buck, HM Henk

doi:10.1021/ja00450a009

Cited by 47 publications

(21 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Extension of this reasoning to organophosphines is probably sound because no multiple bonding between phosphorus and hydrogen is possible and it has generally been accepted that M-H coupling is explained by this mechanism (32). Supporting this view is the observation that 'J(P-H) correlates well with the calculated charges on phosphorus and hydrogen in some protonated phosphites (33).…”

Section: (B) Nuclear Magnetic Resonance Data (I) 'J(p--h) In the Protmentioning

confidence: 95%

The basicity of phosphines

Allman¹,

Goel²

1982

Can. J. Chem.

213

112

View full text Add to dashboard Cite

The basicities of the triarylphosphines P(4-XC6H4)3 (X = Cl, F, H, CH3, CH3O, (CH3)2N), P(3-CH3C6H4)3, and P(2-CH3C6H7)3 as well as the trialkylphosphines P(t-Bu)3 and PCy3 have been measured by the nitromethane titration method. The range of basicity available by aryl substitution is very large, being pKa = 8.65 for X = (CH3)2N to 1.03 for X = Cl. The most basic phosphine is P(t-Bu)3 whose pKa = 11.40. The measured basicities correlate well with σp, [Formula: see text], and ν as well as with the lone pair ionisation potentials of the triarylphosphines. Generally the 1H, 31P, and 13C nmr spectral parameters of the free and protonated phosphines do not correlate well with pKa.

show abstract

Section: (B) Nuclear Magnetic Resonance Data (I) 'J(p--h) In the Protmentioning

confidence: 95%

The basicity of phosphines

Allman¹,

Goel²

1982

Can. J. Chem.

213

112

View full text Add to dashboard Cite

show abstract

“…Phosphorus-based complexes are an important class of compounds in homogeneous catalysis and coordination chemistry (Downing & Smith, 2004;Kü hl, 2005). In particular, we have noted interesting studies comparing the donor ability of bicyclic phosphites and the related acyclic phosphites; the phosphorus atom in the former shows more positive charge than in the acyclic phosphites and, hence, the donor ability of bicyclic phosphites is lower than that of the related acyclic phosphites (Vande Griend et al, 1977;Joslin et al, 2012). The present work is a continuation of an investigation into the synthesis and study of bi-and tri-cyclic, penta-and hexa-coordinated phosphoranes to form anionic, neutral and zwitterionic compounds (Said et al 1996;Timosheva, et al 2006;Kumara Swamy & Satish Kumar, 2006).…”

Section: Chemical Contextmentioning

confidence: 99%

Crystal structure of 4-methyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane

2016

View full text Add to dashboard Cite

show abstract

“…The phosphorus-cobalt couplings in [Co (38) Couplings to phosphorus should increase with increasing positive charge on phosphorus. The higher P-H and ^^Se-P couplings in the protonated and selenated forms, respectively, of bicyclic ligands as opposed to monocyclic phosphites have been explained in this manner (6,7).…”

Section: Stereoretentive Coordination Of 71 and 72 In Cis-mo(c0)4lg Cmentioning

confidence: 99%

“…The value of ^JPH has been related to the s character of the P-H bond (5). It has also been found that more basic phosphorus ligands have a smaller value of ^JPH due to the s electrons being more diffuse because of a smaller positive charge on phosphorus (6). For the same 01 nn reasons P-"Se one-bond couplings in the corresponding selenides can be used as a measure of phosphorus basicity (7).…”

Section: Introductionmentioning

confidence: 99%

“…Possible mechanism of transesterifi cation of 76 upon reaction with Co(II) by equation Series of pseudorotations which isomerize a coordi nated 1,3,2-di oxaphosphori nane the differences which occurred upon the reaction of the two isomeric phosphites 7^_and 7^ may be of either a steric or an electronic nature. It has been shown that for monocyclic phosphites the positive charge on phosphorus is greater when the lone pair of electrons is in an equatorial as opposed to an axial position(6). On this basis, would be expected to undergo nucleophilic attack by methanol more readily than 21.…”

mentioning

confidence: 99%

See 1 more Smart Citation

NMR studies of phosphorus ligand complexes of silver and cobalt

Socol

View full text Add to dashboard Cite

This reproduction was made from a copy of a document sent to us for microfilming. While the most advanced technology has been used to photograph and reproduce this document, the quality of the reproduction is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help clarify markings or notations which may appear on this reproduction. 1.The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting through an image and duplicating adjacent pages to assure complete continuity. 2. When an image on the film is obliterated with a round black mark, it is an indication of either blurred copy because of movement during exposure, duplicate copy, or copyrighted materials that should not have been filmed. For blurred pages, a good image of the page can be found in the adjacent frame. If copyrighted materials were deleted, a target note will appear listing the pages in the adjacent frame. 3. When a map, drawing or chart, etc., is part of the material being photographed, a definite method of "sectioning" the material has been followed. It is customary to begin filming at the upper left hand comer of a large sheet and to continue from left to right in equal sections with small overlaps. If necessary, sectioning is continued again-beginning below the first row and continuing on until complete. 4. For illustrations that cannot be satisfactorily reproduced by xerographic means, photographic prints can be purchased at additional cost and inserted into your xerographic copy. These prints are available upon request from the Dissertations Customer Services Department. 5. Some pages in any document may have indistinct print. In all cases the best available copy has been filmed.

show abstract

Structure-basicity relations among phosphate and phosphite esters. CNDO/2 and protonation studies

Cited by 47 publications

References 0 publications

The basicity of phosphines

The basicity of phosphines

Crystal structure of 4-methyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane

NMR studies of phosphorus ligand complexes of silver and cobalt

Contact Info

Product

Resources

About