Samuel O. Grim

Paramagnetism and shake-up satellites in X-ray photoelectron spectra

Abstract The correlation between paramagnetism and the shake-up satellites in the X-ray photoelectron spectra of the 3d transitional-metal compounds is examined and explained in terms of modified selection rules governing the shake-up transitions.

A phosphorus-31 magnetic resonance study of tertiary phosphine palladium(II) compounds☆

Abstract Phosphorus-31 chemical shifts are reported for thirty-one compounds of the type, cis- and trans-L2PdCl2, sym-L2Pd2Cl4 and trans-L(Am)PdCl2, where L is a tertiary phosphine and Am is a nitrogen ligand. Many of the compounds are previously unreported. For a paticular phosphine ligand the chemical shift of the cis isomer is down-field from that of the trans isomer. Some infrared frequencies and proton nmr results are also given.

An NMR study of arenechromium tricarbonyl complexes

Abstract The high resolution proton magnetic resonance spectrum of 1,4-dimethoxybenzenechromium tricarbonyl furnishes no evidence for a trigonal distortion of the aromatic nucleus in this complex. The PMR and infrared spectra of benzene- and anisole-chromium tricarbonyl and five previously unreported polymethoxybenzenechromium tricarbonyl complexes are also reported and discussed. A simple method for predicting the chemical shifts of the ring protons in both ligands and complexes is presented.

ON THE PHOSPHORUS-31 CHEMICAL SHIFTS OF SUBSTITUTED TRIARYLPHOSPHINES

Abstract The 31P chemical shifts of eleven (4-ZC6H4)3P compounds show a slight correlation with the Hammet [sgrave]para constant of Z. The unusually large upfield chemical shifts of (2-ZC6H4)3P compounds are attributed to an extreme “gamma” effect caused by the restricted conformations due to the steric influence of the ortho substituents. Chemical shifts are given for about thirty triarylphosphines, and group contributions to phosphine chemical shifts are listed for twenty-one aryl groups.

Tertiary phosphine complexes of rhodium(III) and rhodium(I)

Abstract Phosphorus-31 magnetic resonance spectra are reported for twelve compounds of the type mer -[(R n Ph 3−n P) 3 RhCl 3 ], where R is alkyl and n is 1, 2, or 3. The rhodium-103-phosphorus-31 coupling constant is always larger for a phosphine trans to another phosphorus. Coupling between the non-equivalent phosphorus nuclei is also observed. Virtual coupling in the proton magnetic resonance spectra of methyl- and ethyl-phosphine complexes is examined. Visible-ultraviolet spectra are presented.

A PHOSPHORUS-31 NUCLEAR MAGNETIC RESONANCE STUDY OF TERTIARY PHOSPHINE DERIVATIVES OF GROUP VI METAL CARBONYLS. IV. SUBSTITUTED TRIARYLPHOSPHINES

Abstract Thirty compounds of the type (ZC6H4)3PM(CO)5 where Z is 3-CH3, 4-CH3, 3-CH3O, 4-CH3O, 3-CF3, 4-CF3, 4-Cl, 4-F, 4-CH3S, or 4-(CH3) C and M is Cr, Mo, or W are reported, in addition to [4-(CH3)3SiC6H4]3 PW(CO)5 and [(2-CH3C6H4)n(C6H5)3–n P] M(CO)5 where n is 1 or 2 and M is Cr, Mo, or W. Phosphorus-31 NMR and infrared data are presented. In general, the compounds containing the more effective electron withdrawing substituents on the tertiary arylphosphines exhibit the larger 31P coordination chemical shifts, the higher carbonyl stretching frequencies, and the larger phosphorus-31-tungsten-183 coupling constants.

The synthesis and characterization of some novel polydentate phosphorus-nitrogen ligands

Trimethylathylendiamin (I) reagiert mit Diphenylphosphin (II) und Formaldehyd zu den Mannich-Basen (III).

Unsymmetrical Bis-phosphorus Ligands. VI. Synthesis and Characterization of Some Phosphinomethylphosphine Sulfides, (C6H5)2P(S)CH2PR1R2

Abstract Seven novel phosphinomethylphosphine sulfides of the type, (C6H5)2P(S)CH2PR1R2, have been prepared with R1 = C6H5, R2 = C6H5, C2H5, i - C3H7, CH3, N(C2H5)2, and Cl; and with R1 = R2 = i - C3H7. Phosphorus-31 nmr data are reported for the compounds.

Synthesis and phosphorous-31 NMR studies of tertiary arylphosphine complexes of mercury(II) halides

Abstract Several new p -alkyphenylphosphines have been synthesized as well as 12 compounds of the type L 2 HgX 2 and 17 compounds of the type L 2 Hg 2 X 4 where L is a triarylphosphine and X is Cl, Br, or I. Variable temperature phosphorus-31 NMR spectra are reported. The presence or absence and shape of the mercury-199 satellites in the 31 P spectra are a function of the rate of ligand exchange. Qualitatively, the rate of exchange decreases with the increasing basicity of the tertiary phosphine, with decreasing temperature, and with increasing acidity of the mercury species. J Hg−P increases with decreasing temperature for all compounds measured.

PHOSPHORUS-31 MAGNETIC RESONANCE STUDIES OF SOME TERTIARY PHOSPHINE OXIDE COORDINATION COMPOUNDS

Abstract Ten new coordination compounds of the type [Ph2 P(O)CH2 P(O)Ph2 [MX2, where MX2=ZnCl2, CdCl2, CdBr2, CdI2, HgCl2, HgBr2, HgI2, CoCl2, CuCl2, and (CH3)2 SnCl2 are reported. Results of phosphorus-31 nmr studies on these and other monodentate tertiary phosphine oxide complexes are discussed. At ambient temperatures, ligand exchange in solution is rapid for these complexes on the nmr time scale, but dissociation of the bidentate ligand appears to be very slight. Some pmr and infrared data are also presented.