Selenium-77-phoshorus-31 nuclear spin—spin coupling in tri-n-butylphosphine selenide complexes of mercury(II) halides

Grim, Samuel O.; Walton, Edward D.; Satek, Larry C.

doi:10.1016/s0020-1693(00)87249-7

Cited by 12 publications

(5 citation statements)

References 12 publications

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“…a change is known to accompany coordination of phosphine selenides through the selenium atom (23,25). Hence the spectrum is consistent with the formation of Cd(SePPh,),'' with a regular, presumably tetrahedral (at least on a time average), CdSe, core.…”

Section: Resaalts and Discussionmentioning

confidence: 56%

“…Although the IP complexation shifts of phosphine selenides are usually smaller than those of phosphine oxides, a large change in 1 1J(31P-7 7~e ) 1 accompanies complexation (this work and refs. 23,25) and so, if the complexed value is known or can be estimated, the exchange-averaged value of this coupling constant allows determination of the extent of complexation of a phosphine selenide.…”

Section: Competition Between Binaiy Mixtures Ofdiphos-mentioning

confidence: 99%

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A ³¹P nuclear magnetic resonance spectroscopic study of complexes of cadmium(II) with some phosphine oxides, sulfides, and selenides

Dean¹,

Hughes²

1980

Can. J. Chem.

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the ligands Ph,PE (E = S or Se). PhZP(E)(CH,),,P(E)Ph2 ( n = 1 or 2, E = 0. S or Se; n = 3. E = Se). [Ph,P(E)CH,],CMe (E = S or Se) and Ph2P(E)(CH,),PPh(E)(CH,),P(E)PhZ (E = 0, S , or Se) in liquid SOZ has been studied. mainly by low-temperature "P nmr spectroscopy. With the sulfides and selenides the maximum donor atom/Cd ratio observed is four. as shown by the limiting lou temperature spectra of (Ph3PE),Cd2+ (E = S or Se). [CH2(PPh2(Se))l]ZCd", and [PhZP(E)CH2CMe(CH2PPh2(E))2]2CdZ+ (E = S or Se). The laht two complexes both contain apotentially tridentate ligand behaving in a bidentate manner and their spectra are unexpectedly complicated due, perhaps. to conformational effects. Slow exchange spectra of [Ph2P(E)(CH2)2PPh(E)(CH2)2PPh2(E)]CdZ-( E = S or Se) show that in each complex the ligand behaves in a tridentate manner. For the preceding complexes. two-bond l"ll"Cd-'lP coupling is observed at the donor sites. and for the selenides a reduction in 1 1~( 3 '~-7 7~e ) l on complexation further identifies the bound -PSe groups. The maximum coordination number appears to be six in the complexes of the phosphine oxides. Both 2: 1 and 3: 1 L:Cd complexes exist for both of the bidentate ligands Ph2P(0)(CH2),,P(O)Ph2 (rr = I or 2) whereas in the system Ph,P(O) (CH2)2P(0) Ph(CHZ),P(O)Ph,-Cd2-the species identified is the presumably six-coordinate 2: 1 complex. For comparison, the six-coordinate complex [{CHZ(PPh2(0))2}3Hg]2' has been identified in solution also.Competition studies between the dioxides. disulfides. and diselenides ofthe diphosphines show that the disulfides and diselenides cannot compete \+ith the dioxides for cadmium. but that the diselenides can compete with the disulfides to a limited extent.

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Section: Resaalts and Discussionmentioning

confidence: 56%

Section: Competition Between Binaiy Mixtures Ofdiphos-mentioning

confidence: 99%

A ³¹P nuclear magnetic resonance spectroscopic study of complexes of cadmium(II) with some phosphine oxides, sulfides, and selenides

Dean¹,

Hughes²

1980

Can. J. Chem.

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“…These 1 J( 77 Se, 31 P) iso values are all considerably smaller in magnitude than the corresponding solution value of 757 Hz in the 'free' HN( i Pr 2 PSe) 2 ligand. 62 The decrease in the magnitude of 1 J( 77 Se, 31 P) iso values upon complexation has been observed upon coordination of R 3 PSe with Cd(II), 147 or HgX 2 (X = Cl, Br, I), 148 and it has been suggested to result from a lowering of the P-Se bond order upon complexation as the P-Se distance increases from 2.092 and 2.103 A ˚found for the solid-state structure of HN( i Pr 2 PSe) 2 . 62 The complexing strength of [N( i Pr 2 PSe) 2 ] − has been shown in its ability to displace coordinated triphenylphosphine, 149 and a reduction in the magnitude of the phosphorus-selenium coupling constant from the 'free' ligand indicates metal-selenium bonding.…”

Section: Solid-state 77 Se Nmrmentioning

confidence: 98%

A solid-state NMR investigation of single-source precursors for group 12 metal selenides; M[N(ⁱPr₂PSe)₂]₂(M = Zn, Cd, Hg)

Demko

Wasylishen

2008

Dalton Trans.

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The first solid-state NMR investigation of dichalcogenoimidodiphosphinato complexes, M[N(R(2)PE)(2)](n), is presented. The single-source precursors for metal-selenide materials, M[N((i)Pr(2)PSe)(2)](2) (M = Zn, Cd, Hg), were studied by solid-state (31)P, (77)Se, (113)Cd, and (199)Hg NMR at 4.7, 7.0, and 11.7 T, representing the only (77)Se NMR measurements, and in the case of Cd[N((i)Pr(2)PSe)(2)](2)(113)Cd NMR measurements, to have been performed on these complexes. Residual dipolar coupling between (14)N and (31)P was observed in solid-state (31)P NMR spectra at 4.7 and 7.0 T yielding average values of R((31)P,(14)N)(eff) = 880 Hz, C(Q)((14)N) = 3.0 MHz, (1)J((31)P,(14)N)(iso) = 15 Hz, alpha = 90 degrees , beta = 26 degrees . The solid-state NMR spectra obtained were used to determine the respective phosphorus, selenium, cadmium, and mercury chemical shift tensors along with the indirect spin-spin coupling constants: (1)J((77)Se,(31)P)(iso), (1)J((111/113)Cd,(77)Se)(iso), (1)J((199)Hg,(77)Se)(iso), and (2)J((199)Hg,(31)P)(iso). Density functional theory magnetic shielding tensor calculations were performed yielding the orientations of the corresponding chemical shift tensors. For this series of complexes the phosphorus magnetic shielding tensors are essentially identical, the selenium magnetic shielding tensors are also very similar with respect to each other, and the magnetic shielding tensors of the central metals, cadmium and mercury, display near axial symmetry demonstrating an expected deviation from local S(4) symmetry.

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“…We report here the results of an nmr (31P) study on the complexes of some tertiary phosphine selenide and sulfide complexes with mercury(I1) and cadmium(I1) halides. A preliminary communication of this work has already appeared (6). In spite of the fact that these coordination complexes are very simple addition compounds, many of them have not been previously reported and characterized.…”

mentioning

confidence: 99%

Mercury(II) and cadmium(II) halide complexes of tertiary phosphine sulfides and selenides

Grim¹,

Walton²,

Satek³

1980

Can. J. Chem.

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Phosphorus-31 nmr data are reported for tri-n-butylphosphine selenide complexes of mercury(II) and cadmium halides and for some miscellaneous complexes of tertiary phosphine sulfides and selenides with the same metal halides. The ligands in the complexes are labile in solution at room temperature but the exchange can be "frozen out" in certain cases at reduced temperature. Selenium-77–phosphorus-31 coupling constants are less in the complexes than in the free ligands and 1JPSe decreases in each observable case with decreasing temperature. Two bond mercury-199–phosphorus-31 coupling is observed in some of the cooled solutions of the complexes.

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Selenium-77-phoshorus-31 nuclear spin—spin coupling in tri-n-butylphosphine selenide complexes of mercury(II) halides

Cited by 12 publications

References 12 publications

A ³¹P nuclear magnetic resonance spectroscopic study of complexes of cadmium(II) with some phosphine oxides, sulfides, and selenides

A ³¹P nuclear magnetic resonance spectroscopic study of complexes of cadmium(II) with some phosphine oxides, sulfides, and selenides

A solid-state NMR investigation of single-source precursors for group 12 metal selenides; M[N(ⁱPr₂PSe)₂]₂(M = Zn, Cd, Hg)

Mercury(II) and cadmium(II) halide complexes of tertiary phosphine sulfides and selenides

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Selenium-77-phoshorus-31 nuclear spin—spin coupling in tri-n-butylphosphine selenide complexes of mercury(II) halides

Cited by 12 publications

References 12 publications

A 31P nuclear magnetic resonance spectroscopic study of complexes of cadmium(II) with some phosphine oxides, sulfides, and selenides

A 31P nuclear magnetic resonance spectroscopic study of complexes of cadmium(II) with some phosphine oxides, sulfides, and selenides

A solid-state NMR investigation of single-source precursors for group 12 metal selenides; M[N(iPr2PSe)2]2(M = Zn, Cd, Hg)

Mercury(II) and cadmium(II) halide complexes of tertiary phosphine sulfides and selenides

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A ³¹P nuclear magnetic resonance spectroscopic study of complexes of cadmium(II) with some phosphine oxides, sulfides, and selenides

A ³¹P nuclear magnetic resonance spectroscopic study of complexes of cadmium(II) with some phosphine oxides, sulfides, and selenides

A solid-state NMR investigation of single-source precursors for group 12 metal selenides; M[N(ⁱPr₂PSe)₂]₂(M = Zn, Cd, Hg)