Phosphorus-phosphorus spin-spin coupling in metal carbonyl complexes of phosphorus trifluoride

Ogilvie, F. B.; Clark, Ronald J.; Verkade, J. G.

doi:10.1021/ic50079a020

Cited by 26 publications

(6 citation statements)

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“…The correlation of effective nuclear charge and hybridization changes with coupling constants in bicyclic phosphorus molecules and their derivatives has been discussed in other publications, and the arguments will not be repeated here. [33][34][35] Figure 3 reveals that VPH becomes negative upon increasing the Lewis acidity of Y over a range of ca. 15 Hz for classes B and C, whereas a range of less than ca.…”

Section: Discussionmentioning

confidence: 99%

Nuclear magnetic resonance studies of some novel metal carbonyl complexes and other derivatives of 2,6,7-trioxa-1,4-diphospha-bicyclo[2.2.2]octane

Bertrand¹,

Allison²,

Verkade³

1970

J. Am. Chem. Soc.

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The novel coordination properties of the nonchelating bifunctional phosphorus ligand P(OCH2)3P have allowed the characterization of (OC)6MP(OCH2)3P and (0C)5MP(0CH2)3PM(C0)5 (M = Cr, Mo, and W); axial (OC)4FeP(OCH2)3P, axial (0C)4FeP(CH20)3P, and diaxial (OC)4FeP(OCH2)3PFe(CO)4; [CH3P(OCH2)3P]BF4 and [P(OCH2)3PCH3]BF4; and [(OC)5WP(OCH2)aPCH3]BF4. The mode of coordination of the ligand in the monometallic and phosphonium compounds was determined from the characteristic changes in the P81 chemical shifts and the PH and PP coupling constants. These methods were also used to characterize the unusual nonaxial (OC)4FeP(OCH2)3P (see ref 18). The magnitudes and signs of the VPH, Vph, and 37PP coupling constants in all of the compounds were obtained from the proton nmr spectra using indor techniques where appropriate. The trends in these parameters as the electron-withdrawing power of the fourth group attached to phosphorus increases in the order, electron pair < metal carbonyl fragment < methyl group < chalcogen, are interpreted in terms of the expected changes in nuclear charge of the atoms and s character of the bonds in the ligand. Infrared studies indicate that quaternization of the ligand in [(OC5)WP(OCH2)3P] to form [(OC)sP(OCH2)3PCH3]BF4 does not detectably alter the overall nature of the tungsten-phosphorus bond.

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Section: Discussionmentioning

confidence: 99%

Nuclear magnetic resonance studies of some novel metal carbonyl complexes and other derivatives of 2,6,7-trioxa-1,4-diphospha-bicyclo[2.2.2]octane

Bertrand¹,

Allison²,

Verkade³

1970

J. Am. Chem. Soc.

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“…32 The few structural data available on phosphorus ligands and their derivatives seem to be consistent with the idea that the substituent-phosphorussubstituent angles on the ligand very likely decrease with increasing electronegativity of the substituent in coordination complexes. 33 Although the x-bonding capacity of ligands is generally believed to be a factor which partially controls carbonyl stretching frequencies in LM(CO)e molecules (M = Mo, W),14'16•28 it has been postulated that basicity arguments alone adequately explain certain trends in carbonyl stretching frequencies.19 Moreover, intensity studies suggest that substituting L for a CO group in an M(CO)6 molecule decreases C-0 bonding by weakening the M-C bonds without appreciably altering the M-C x bonding. 34 The extent to which the CO stretching frequencies of the carbonyl groups decrease upon substitution by L will depend upon the extent to which the energy of the x orbitals on the metal are lowered which in turn depends upon both thedonating and the x-accepting capacities of the ligand.…”

Section: Discussionmentioning

confidence: 99%

Tungsten-183-phosphorus-31 spin-spin coupling interactions in pentacarbonyltungsten complexes

Keiter¹,

Verkade²

1969

Inorg. Chem.

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“…Syntheses. The phosphane complexes M(CO) 5 PH 3 and M(CO) 5 PF 3 (M = Cr, Mo, W) have been prepared earlier either by photochemical , or by thermal substitution from the metal hexacarbonyls and the ligands as precursors. As a rule, labile compounds such as M(CO) 5 (THF) and M(CO) 5 (CH 2 Cl 2 ) were used as intermediates.…”

Section: Methodsmentioning

confidence: 99%

Nature of the Metal−Ligand Bond in M(CO)₅PX₃ Complexes (M = Cr, Mo, W; X = H, Me, F, Cl): Synthesis, Molecular Structure, and Quantum-Chemical Calculations

et al. 2002

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The syntheses of the phosphane complexes M(CO)5PH3 (M = Mo, W), W(CO)5PD3, and W(CO)5PF3 and the results of X-ray structure analyses of W(CO)5PH3 and Mo(CO)5PCl3 are reported. Quantum-chemical DFT calculations of the geometries and M−P bond dissociation energies of M(CO)5PX3 (M = Cr, Mo, W; X = H, Me, F, Cl) have been carried out. There is no correlation between the bond lengths and bond dissociation energies of the M−P bonds. The PMe3 ligand forms the strongest and the longest M−P bonds of the phosphane ligands. The analysis of M−PX3 bonds shows that PCl3 is a poorer σ donor and a stronger π(P) acceptor than the other phosphanes. The energy decomposition analysis indicates that the M−P bonds of the PH3 and PMe3 complexes have a higher electrostatic than covalent character. The electrostatic contribution is between 56 and 66% of the total attractive interactions. The orbital interactions in the M−PH3 and M−PMe3 bonds have more σ character (65−75%) than π character (25−35%). The M−P bonds of the halophosphane complexes M(CO)5PF3 and M(CO)5PCl3 are nearly half covalent and half electrostatic. The π bonding contributes ∼50% to the total orbital interaction.

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Phosphorus-phosphorus spin-spin coupling in metal carbonyl complexes of phosphorus trifluoride

Cited by 26 publications

References 1 publication

Nuclear magnetic resonance studies of some novel metal carbonyl complexes and other derivatives of 2,6,7-trioxa-1,4-diphospha-bicyclo[2.2.2]octane

Nuclear magnetic resonance studies of some novel metal carbonyl complexes and other derivatives of 2,6,7-trioxa-1,4-diphospha-bicyclo[2.2.2]octane

Tungsten-183-phosphorus-31 spin-spin coupling interactions in pentacarbonyltungsten complexes

Nature of the Metal−Ligand Bond in M(CO)₅PX₃ Complexes (M = Cr, Mo, W; X = H, Me, F, Cl): Synthesis, Molecular Structure, and Quantum-Chemical Calculations

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Phosphorus-phosphorus spin-spin coupling in metal carbonyl complexes of phosphorus trifluoride

Cited by 26 publications

References 1 publication

Nuclear magnetic resonance studies of some novel metal carbonyl complexes and other derivatives of 2,6,7-trioxa-1,4-diphospha-bicyclo[2.2.2]octane

Nuclear magnetic resonance studies of some novel metal carbonyl complexes and other derivatives of 2,6,7-trioxa-1,4-diphospha-bicyclo[2.2.2]octane

Tungsten-183-phosphorus-31 spin-spin coupling interactions in pentacarbonyltungsten complexes

Nature of the Metal−Ligand Bond in M(CO)5PX3 Complexes (M = Cr, Mo, W; X = H, Me, F, Cl): Synthesis, Molecular Structure, and Quantum-Chemical Calculations

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Nature of the Metal−Ligand Bond in M(CO)₅PX₃ Complexes (M = Cr, Mo, W; X = H, Me, F, Cl): Synthesis, Molecular Structure, and Quantum-Chemical Calculations