✍ Scribed by Rainer Soltek; Gottfried Huttner
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Tripod ligands RCH 2 C(CH 2 PPh 2 )(CH 2 X)(CH 2 Y) (1) with X, strongly coordinate in compounds such as [η 3 -{CH 3 C(CH 2 PPh 2 ) 2 (CH 2 S)}(CO) 3 Mo] -which are obtained as Y = SAlkyl, SBzl selectively undergo reductive cleavage of the SBzl function with Li/NH 3 /THF at -40 °C to produce their lithium and sodium salts 6. These highly reactive species may be stabilized by encapsulating their alkali RCH 2 C(CH 2 PPh 2 )(CH 2 X)(CH 2 Y) (2) (X, Y = SAlkyl, SH). In these mixed donor set ligands the SH functions are the least counter ions in cryptands and the corresponding salts with [2,1,1]cryptand (7a) and [2,2,2]cryptand (7b) are far easier to coordinative ones such that [η 2 -{CH 3 C(CH 2 PPh 2 )(CH 2 SEt)-(CH 2 SH)}(CO) 4 Mo] (5) is a stable compound with an handle than the cryptand-free progeners 6. Alkylation of the coordinatively bound thiolate function in 6 leads to the uncoordinated SH function at the dangling arm of the ligand. If the SH functions of a potential tripod ligand are corresponding thioether derivatives [η 3 -{CH 3 C(CH 2 PPh 2 ) 2 -(CH 2 SR)}(CO) 3 Mo] (8). deprotonated the resulting thiolate functions are found to
📜 SIMILAR VOLUMES
The chlorine functions of CH 3 C(CH 2 Cl) 3 , 1, may be replaced involved in intramolecular hydrogen bonding to the CH 2 OH function (N•••H-O distance 280 pm). Blocking of the OH by pyrazolyl (pz) as well as imidazolyl (im) residues under the conditions of nucleophilic substitution leading to tripod
Functionalized tripod ligands / Mixed donor set ligands / Solubilized tripod ligands / Molybdenum / Iron / Neopentane-derived tripod ligands of the general type electrophiles will produce the corresponding ether derivatives ROCH 2 C(CH 2 PPh 2 )(CH 2 Z) 2 (3). Mesylation of 2 HOCH 2 C(CH 2 PPh 2 )(C
Rotational barriers and π conjugation effects have been SCH 3 species. An acute B-S-C angle (69.6°) is found, thus evidencing a direct H•••B agostic interaction with a four-studied in H 2 X-YR systems (X = Al, B; Y = O, S; R = H, CH 3 ) by means of ab initio calculations at the MP4/6-311G\*\*// memb