Rhodium induced titanium–sulfur bond cleavage: crystal and molecular structure of ((COD)Rh(μ-SMe))₂

Abstract

. Can. J. Chem. 68, 565 (1990) The structural data show a relatively short approach between the Rh centres (2.948 A) and between the bridging sulfur atoms (2.888 A). The implications of these structural features in terms of metal-metal and sulfur-sulfur bonding are discussed. In addition, the implications of these results with respect to the formation of thiolato-bridged, early-late heterobimetallics is considered.Key words: thiolate abstraction, rhodium thiolate bridged dimer.

Silsesquioxanes as models of silica supported catalyst I. [3‐(Diphenylphosphino)propyl]‐hepta[propyl]‐[octasilsesquioxane] and [3‐mercapto‐propyl]‐hepta[propyl]‐[octasilsesquioxane] as ligands for transition‐metal ions

“…1) give rise to clearly distinguishable 29 Si NMR spectra. 14 The assignment is furthered by 29 Si 2D INADEQUATE NMR spectroscopy. The 2 J(Si-O-Si) coupling is below 1 Hz.…”

“…The substitution patterns of mixed substituted octa(organosilsesquioxanes) ( Fig. 1) give rise to clearly distinguishable 29 Si NMR spectra. 14 The assignment is furthered by 29 Si 2D INADEQUATE NMR spectroscopy.…”

“…The 29 Si signal from the X(CH 2 ) 3 Si segment (intensity = 1) is found most often upfield of the H(CH 2 ) 3 Si groups. The 29 Si NMR data for the cages are collected in Table 1.…”

“…[16][17][18] The reaction of dpps with [Rh(CO) 2 The 31 P NMR spectrum of the complex gives a doublet at = 22.83 ppm with splitting due to 1 J(Rh,P) = 124.9 Hz compatible with a trans configuration of the phosphine ligands. 19,20 The triplet in the 29 Si spectrum can be explained by coupling with both phosphorus atoms. Coupling with the rhodium atom is too small to be observed.…”

“…A value of 1 J(Pt,P) = 3636 Hz is typical for cis-configured platinum complexes of this kind. 5 The 29 Si signal for the Si(CH 2 ) 3 X part is a triplet because of coupling with two phosphorus atoms. The signals of the 2-,4-and 5-silicon atoms of the silsesquioxane cage are shifted to higher fields and found at = À66.63 ppm, whereas the 3-,6-and 8-silicon atoms resonate at = À66.54 ppm and that in the 7-position at = À66.56 ppm.…”