Cationic rhodium(I) sulfoxide complexes. Synthesis and spectroscopic properties

1977 ◽  
Vol 55 (12) ◽  
pp. 2353-2359 ◽  
Author(s):  
Brian R. James ◽  
Robert H. Morris ◽  
Kenneth J. Reimer
Keyword(s):  
Transition Metal ◽  
Frequency Shift ◽  
Spectroscopic Properties ◽  
Alkyl Aryl ◽  
H Nmr ◽  
Methyl Sulfoxide ◽  
Solid Compounds ◽  
Oxygen Bond ◽  
Infrared Data ◽  
Methyl Phenyl

Displacement of the labile acetone ligand from [Rh(diene)(PPh3)(acetone)]A (diene = 1,5-cyclooctadiene (COD), norbornadiene (NBD); A = PF6−, SbF6−) allows facile coordination of dialkyl or alkyl aryl sulfoxides, and [Rh(diene)(PPh3)(sulfoxide)]+ complexes have been synthesized using dimethyl sulfoxide (DMSO), tetramethylene sulfoxide (TMSO), di-n-propyl sulfoxide (NPSO), (S,S;S,R)-(+)-2-methylbutyl methyl sulfoxide (MBMSO), methyl phenyl sulfoxide (MPSO), (R)-(+)-methyl-p-tolyl sulfoxide (MPTSO), and (R)-t-butyl p-tolyl sulfoxide (TBPTSO).Diaryl sulfoxides appear to coordinate in solution but no solid compounds could be isolated. The upfield shifts of the sulfoxide resonances (1H nmr), reflecting shielding by the adjacent phenyl groups of PPh3, and the decrease in ν(SO) on coordination, are indicative of O-bonding in all cases. Infrared data indicate that the frequency shift of ν(SO) upon O-coordination is roughly proportional to the strength of the metal–oxygen bond for a range of transition metal DMSO and TMSO complexes.

Preparation, properties and structure of some intermediate nido- and arachno-monocarbaboranes

1981 ◽  
Vol 46 (10) ◽  
pp. 2345-2353 ◽  
Author(s):  
Karel Baše ◽  
Bohumil Štíbr ◽  
Jiří Dolanský ◽  
Josef Duben
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Nmr Spectra ◽  
Liquid Ammonia ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Starting Compound

The 6-N(CH3)3-6-CB9H11 carbaborane reacts with sodium in liquid ammonia with the formation of 6-CB9H12- which was used as a starting compound for preparing the 4-CB8H14, 9-L-6-CB9H13 (L = (CH3)2S, CH3CN and P(C6H5)3), 1-(η5-C5H5)-1,2-FeCB9H10-, and 2,3-(η5-C5H5)2-2,31-Co2CB9H10- carboranes. The 4-CB8H14 compound was dehydrogenated at 623 K to give 4-(7)-CB8H12 carborane. Base degradation of 6-N(CH3)3-6-CB9H11 in methanol resulted in the formation of 3,4-μ-N(CH3)3CH-B5H10. The structure of all compounds was proposed on the basis of their 11B and 1H NMR spectra and X-ray diffraction was used in the case of the transition metal complexes.

Triazolopyridine nucleosides. II. Glycosylations of 3-oxo-s-triazolo[4,3-a]pyridines with accompanying conversions into 2-oxo-s-triazolo[1,5-a]pyridine nucleosides

1977 ◽  
Vol 55 (5) ◽  
pp. 831-840 ◽  
Author(s):  
Brian Maurice Lynch ◽  
Suresh Chandra Sharma
Keyword(s):  
General Structure ◽  
Spectroscopic Properties ◽  
Mass Spectral Fragmentation ◽  
Mass Spectral ◽  
H Nmr ◽  
Pyridine Nitrogen ◽  
Methyl Derivatives ◽  
Fragmentation Patterns ◽  
Ribose Moiety ◽  
C Nmr

3-Oxo-s-triazolo[4,3-a]pyridine and various C-methyl derivatives (general structure 1) have been converted into the 2-β-D-ribofuranosyl species 2 and thence 4 via Friedel–Crafts catalyzed reaction with tetra-O-acetyl-β-D-ribofuranose, followed by deblocking. During the course of these reactions, rearrangements into the isomeric 3-β-D-ribofuranosyl-2-oxo-s-triazolo[1,5-a]-pyridines occur through ring-opening of the pyridine rings yielding species 3 and 5. The proportion of rearrangement products is dependent upon the position and number of the C-methyl substituents.Structural assignments for these compounds are based upon comparisons of spectroscopic properties (1H nmr, 13C nmr, uv) with model compounds from each isomeric series; structural assignments for these models are based on unequivocal mass-spectral fragmentation patterns. Unlike related triazolopyridine nucleosides with the ribose moiety attached to a pyridine nitrogen (Lynch and Sharma (1976)), there are no unusual aspects in the conformations of the nueleosides of types 4 and 5.

Transition-Metal-Catalyzed Transformation of Sulfonates via S–O Bond Cleavage: Synthesis of Alkyl Aryl Ether and Diaryl Ether

2019 ◽  
Vol 21 (22) ◽  
pp. 8879-8883 ◽  
Author(s):  
Xuemeng Chen ◽  
Xue Xiao ◽  
Haotian Sun ◽  
Yue Li ◽  
Haolin Cao ◽  
...  
Keyword(s):  
Transition Metal ◽  
Bond Cleavage ◽  
Aryl Ether ◽  
Alkyl Aryl ◽  
Diaryl Ether ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

scholarly journals Übergangsmetall-substituierte VB Elementsysteme, 7.

1975 ◽  
Vol 30 (3-4) ◽  
pp. 229-234 ◽  
Author(s):  
Wolfgang Malisch ◽  
Peter Panster
Keyword(s):  
Transition Metal ◽  
Mass Spectroscopy ◽  
Bond Cleavage ◽  
Metal Carbonyl ◽  
Metal Carbonyls ◽  
H Nmr ◽  
Complex Metal ◽  
Stable Species ◽  
New Compounds

The reaction of SbBr3 with the complex metal carbonyl anions [π-C5H6(CO)3M]Na (M = Mo, W) leads to the formation of transition metal antimony bromides π-C5H5(CO)3M-Sb̅-Br2, which can be further metallated, yielding the stable species [XXX]All bromine substituted transition metal stibines prove to be excellent coordinating ligands and can easily be introduced into activated metal carbonyls. The interaction of π-C5H5(CO)3M-Sb̅Br2, with bromine results in a quantitative Sb-M bond cleavage, presumably via primary formation of pentavalent intermediates. All new compounds are fully characterized by means of IR, 1H NMR and mass spectroscopy.

The planar conformation of 2-methylthiobenzaldehyde in solution

1983 ◽  
Vol 61 (1) ◽  
pp. 26-28
Author(s):  
Ted Schaefer ◽  
Rudy Sebastian
Keyword(s):  
Chemical Shifts ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Spectral Parameters ◽  
H Nmr ◽  
Heavy Atoms ◽  
Planar Conformation ◽  
Spin Coupling Constants ◽  
Spin Spin Coupling ◽  
Infrared Data

The 1H nmr spectral parameters are extracted for a 4 mol% solution of 2-methylthiobenzaldehyde in CCl4 at 305 K. The long-range spin–spin coupling constants involving the aldehydic and methyl protons are consistent only with a preferred conformation in which all heavy atoms are coplanar, as are the chemical shifts of the ring and methyl protons. This conclusion contradicts previous interpretations of the dipole moment, the nmr parameters, and of the infrared data for CCl4 solutions. The present data show that the O-syn and O-anti forms of the compound are present in roughly equal proportions.

Sign in / Sign up

Export Citation Format

Share Document