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

Keiter, Richard L.; Verkade, John G.

doi:10.1021/ic50080a015

Cited by 73 publications

(20 citation statements)

References 6 publications

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“…Again, this trend was also found for the corresponding tungsten complexes [21], and correlated to the decreasing o-donating capacity of the coordinated phosphorus atom. Other factors influencing the magnitude of /, such as the cone angle [20], the ionization potential of the metal, or the partial charge on the phosphorus nucleus and its polarizabilitv must be considered as discussed at length in [13].…”

Section: Methodssupporting

confidence: 56%

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⁶³Cu FT-NMR Studies of Tetrahedral Copper(I)-Phosphorus Complexes

Kroneck¹,

Lutz²,

Nolle³

et al. 1980

Zeitschrift Für Naturforschung A

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Tetrahedrally coordinated copper(I) complexes C11L4X have been synthesized, L being P(OR)3, PR3 or P(R)n(OR)3-n, and X being a non-coordinating anion such as Perchlorate or tetrafluoroborate. Depending on the nature of the bound phosphorus ligand the Cu(I) complexes give well resolved 63 Cu NMR spectra including a quintet signal due to spin-spin coupling between 63 Cu and 31 P. The 63 Cu NMR spectra have been analyzed with reference to the chemical shift (), the shielding constant a* (given on an absolute atomic scale), the linewidth Av, and the coupling constant J( 63 Cu-31 P). Generally, the relative magnitude of these NMR parameters are in satisfactory agreement with results reported for isoelectronic Ni(O) complexes with the phosphorus ligands mentioned above. Furthermore, the NMR properties of the Cu(I) compounds are discussed in terms of cr-donor or 7r-acceptor capacities of the ligands coordinated, and stereochemical properties of the complexes.

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Section: Methodssupporting

confidence: 56%

“…[1] R. K. Harris and B. E. Mann, NMR and the Periodic Verkade [21]. Again, this trend was also found for the corresponding tungsten complexes [21], and correlated to the decreasing o-donating capacity of the coordinated phosphorus atom.…”

Section: Methodsmentioning

confidence: 80%

⁶³Cu FT-NMR Studies of Tetrahedral Copper(I)-Phosphorus Complexes

Kroneck¹,

Lutz²,

Nolle³

et al. 1980

Zeitschrift Für Naturforschung A

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“…The | 1 J P–Se | values of selenium complexes of P‐donor ligands can be used to estimate their σ‐donor capacity (Lewis basicity) because the magnitude of | 1 J P–Se | depends on both the electronegativity and steric congestion of the substituents of the phosphorus , . There is an inverse relationship between the σ‐basicity and the | 1 J P–Se | of the phosphorus as illustrated by the following series of | 1 J P–Se | values: P(OPh) 3 (1027 Hz) < P(pyrrolyl) 3 (970 Hz) < P(OMe) 3 (954 Hz) < P(Ph) 2 (pyrrolyl) (812 Hz) < P(Ph) 3 (736 Hz) < P(Me) 3 (684 Hz) .…”

Section: Resultsmentioning

confidence: 99%

Comparative Study of Novel Phosphordiamidite and Phosphite Ligands Used in Alkene Hydroformylation; Synthesis, Characterization, Metalation, and Catalytic Evaluation

et al. 2018

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Three novel ligands have been prepared by the reactions of 1,1′-(chlorophosphinediyl)bis(1H-pyrrole) with either 2pyridinemethanol or 2,6-pyridinedimethanol or the reaction of 1,1′-biphenyl-2,2′-diyl phosphorochloridite with 2-pyridinemethanol. Measurement of | 1 J P-Se | values demonstrate that the phosphite donor is less basic than the phosphoramidite donors. Coordination preferences of the ligands in octahedral cis-tetracarbonylmolybdenum(0) and square planar cis-dichloropalladium(II) complexes have been evaluated using multinuclear NMR and X-ray crystallography. Rhodium(I) complexes of the Scheme 2. Synthesis of chelating molybdenum complexes 1-3.Scheme 3. Synthesis of palladium chelating complexes 4, 5 and 6.

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“…Cis-[Mo(CO) 4 (PR 3 ) 2 ] complexes give A 1 carbonyl stretching frequencies that correlate linearly with those found in the extensively studied [Ni(CO) 3 (PR 3 )] series of compounds [25], evading the need to use the highly toxic [Ni(CO) 4 ] precursor and are thus particularly attractive [26]. [W(CO) 5 (PR 3 )] complexes have also been prepared and their 31 P-183 W NMR coupling constants have been shown to increase linearly with the stretching frequencies of the carbonyl E mode [27], and although this correlation was found to be weak for a different series of complexes prepared by Keiter and Verkade [28], they did establish a linear relationship between higher values of coupling constant and a greater electronegativity of the substituents on the phosphorus donor, which was discussed further by McFarlane et al [29]. In addition, tungsten carbonyl complexes have been used to stabilize alkyl primary phosphines that have not been observed in the free state [11b, 30] and primary alkynyl and allenylphosphines that are otherwise highly unstable [11b, 31].…”

Section: Molybdenum and Tungsten Carbonyl Complexes Of The Fluorescenmentioning

confidence: 99%

Air-stable fluorescent primary phosphine complexes of molybdenum and tungsten

Davies

Wallis

Harrington

et al. 2016

Journal of Coordination Chemistry

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Here we report a study on the reactivity of the fluorescent air-stable primary phosphine 8-((4-phosphino)phenyl)-4,4-dimethyl-1,3,5,7-tetramethyl-2,6-diethyl-4-bora-3a,4a-diaza-s-indacene 4 with [Mo (CO) 6 ], [W(CO) 6 ], [Mo(CO) 4 (piperidine)] and [W(CO) 4 (piperidine)] which yields the mono-phosphine [Mo(CO) 5 (4)] 5, [W(CO) 5 (4)] 6 and di-phosphine cis-[Mo(CO) 4 (4) 2 ] (7) and cis-[W(CO) 4 (4) 2 ] (9) complexes as the predominant products. In addition to the characterisation of these complexes by multinuclear NMR and IR spectroscopy, and mass spectrometry, the solid state structures of 6 and cis-7 have also been determined by single crystal X-ray diffraction. The photophysical properties of the complexes show that the incorporation of the phosphorus ligand has a limited effect on the absorption and emission profile of the Bodipy core and that they retain similar quantum yields to their parent Bodipy dyes. Small quantities of the by-products trans-[Mo(CO) 4 (4) 2 ] (7), cis-[Mo(CO) 4 (piperidine)(4)] (8) and cis-[W(CO) 4 (piperidine)(4)] (10) were also isolated and characterized.

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

Cited by 73 publications

References 6 publications

⁶³Cu FT-NMR Studies of Tetrahedral Copper(I)-Phosphorus Complexes

⁶³Cu FT-NMR Studies of Tetrahedral Copper(I)-Phosphorus Complexes

Comparative Study of Novel Phosphordiamidite and Phosphite Ligands Used in Alkene Hydroformylation; Synthesis, Characterization, Metalation, and Catalytic Evaluation

Air-stable fluorescent primary phosphine complexes of molybdenum and tungsten

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

Cited by 73 publications

References 6 publications

63Cu FT-NMR Studies of Tetrahedral Copper(I)-Phosphorus Complexes

63Cu FT-NMR Studies of Tetrahedral Copper(I)-Phosphorus Complexes

Comparative Study of Novel Phosphordiamidite and Phosphite Ligands Used in Alkene Hydroformylation; Synthesis, Characterization, Metalation, and Catalytic Evaluation

Air-stable fluorescent primary phosphine complexes of molybdenum and tungsten

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⁶³Cu FT-NMR Studies of Tetrahedral Copper(I)-Phosphorus Complexes

⁶³Cu FT-NMR Studies of Tetrahedral Copper(I)-Phosphorus Complexes